Photoredox Catalyzed Strain-Release Driven Synthesis of

Functionalized Spirocyclobutyl Oxindoles

Tushar Singha,† Nakul Abhay Bapat,† Subrat Kumar Mishra† and Durga Prasad Hari*
Department of Organic Chemistry, Indian Institute of Science, Bangalore, India, 560012
Email: [email protected]
(†Authors contributed equally)

Table of Contents

1. General methods S2

2. Procedures for starting materials synthesis S3

3. Optimization and Procedures for the photocatalytic reactions S31

4. Characterization of new compounds S33

5. Procedures for Reaction scale up and product modifications S61

6. Radical trapping, fluorescence quenching and cyclic voltammetry experiments S63

7. Crystallography data S66

8. DFT calculations S68

9. References S85

10. NMR spectra for new compounds S86

S1
1. General methods
1.1 Solvents, Reagents, Glassware and Reaction Setup
Unless otherwise specified, all reactions were conducted under an inert atmosphere of nitrogen
or argon using hot air oven dried (120 ºC) glassware utilizing standard Schlenk-line technique.
Air- and moisture-sensitive liquids and solutions were transferred via syringe into the reaction
vessels through a rubber septum under inert atmosphere. Unless otherwise specified, all
reagents were purchased at highest commercial quality and used as received. Non-anhydrous
solvents were purchased at the highest commercial quality and used as received. Organic
solvents used for carrying out reactions were dried using standard methods. All work up and
purification were carried out with reagent grade solvents in air.

1.2 Analytical methods

Chromatography: Column chromatography was carried out using Sigma-Aldrich silica gel
(60 Å, 230-400 mesh, 40-63 μm). Reactions were monitored by thin-layer chromatography
(TLC), using aluminium-backed Merck Kieselgel 60 F254 fluorescent treated silica gel plates,
which were visualized under UV light or by staining with aqueous basic KMnO4. IR: Infrared
(FT-IR) spectra were recorded of neat sample on Bruker alfa FT-IR, νmax in cm‒1 and the bands
are characterized as strong (s), medium (m), and weak (w). Melting Point: Melting points were
measured in open glass capillary on a Buchi M-560 melting point apparatus. NMR: NMR
spectra were recorded on Bruker Ultrashield spectrometer at 400 MHz and 600 MHz (for 1H-
NMR), 101 MHz and 151 MHz (for 13C-NMR), 376 MHz (for 19F-NMR), 162 MHz and 243
MHz (31P-NMR). Chemical shifts are reported in ppm from tetramethylsilane with the solvent
resonance as internal standard (CDCl3: δ 7.26 ppm for 1H-NMR and δ 77.00 ppm for 13
C-
NMR). For 1H-NMR, data are reported as follows: chemical shift, multiplicity (s = singlet, brs
= broad singlet, d = doublet, dd = doublet of doublets, ddd = doublet of doublet of doublets, t
= triplet, q = quartet, dt = doublet of triplets, m = multiplet etc.), coupling constants (Hz) and
integration. NMR yields: Following work up or/and solvent evaporation,
dibromomethane/PhCF3 (relative to limiting starting material) was added to the crude residue.
The resultant mixture was dissolved in CDCl3, and a 0.5 mL sample of the resultant solution
taken for 1H NMR analysis. Yields were calculated based on the integrals of known product
resonances relative to dibromomethane (2H, at 4.94 ppm in CDCl3). MS: High Resolution
Mass Spectrometry (HRMS) was performed on Waters e2695 XEVO G2-XS Q-TOF
instrument.

S2
2. Procedures for starting materials synthesis

2.1 Synthesis of bicyclo[1.1.0]butanes (BCBs)

BCB amides (1a-1h) were synthesized using the following procedures.

N-Methyl-N-phenylbicyclo[1.1.0]butane-1-carboxamide (1a)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, N-methylaniline (0.49 mL, 4.5 mmol, 0.90 equiv) and
triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom flask
and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution, crude
acyl chloride was added dropwise. Then, the reaction mixture was warmed to room temperature

S3
and further stirred overnight. Next, the reaction mixture was quenched with a saturated aqueous
NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The combined organic layers
were dried over MgSO4, and the solvent was evaporated under reduced pressure to obtain the
compound 10 as a brown liquid (744 mg, 3.66 mmol, 73%). This crude compound was used in
the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone (744 mg, 3.66 mmol, 1.00 equiv)
and MeOH (15 mL, 0.24 M). The resulting solution was cooled to 0 °C, and NaBH4 (111 mg,
2.92 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the reaction
mixture was quenched with a saturated aqueous NH4Cl solution (20 mL) and extracted with
DCM (3×10 mL). The combined organic phases were washed with brine (25 mL) and dried
over Na2SO4. The solvent was removed under vacuum to afford the product 11 as light-yellow
oil (713 mg, 3.47 mmol, 95%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol (713 mg, 3.47
mmol, 1.00 equiv) and dry DCM (10 mL, 0.35 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (1.2 g, 6.2 mmol, 1.8 equiv)
and Et3N (0.63 mL, 4.5 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 12 as a pale-yellow oil (861 mg, 2.40 mmol,
69%). The crude product was used in the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product (861
mg, 2.40 mmol, 1.00 equiv) and THF (12 mL, 0.20 M) under inert atmosphere. Then, the
solution was cooled to 0 °C and a solution of KOtBu (403 mg, 3.59 mmol, 1.50 equiv) in THF
(5 mL, 0.73 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for
30–60 mins. The reaction mixture was monitored by TLC to confirm the complete consumption
of the starting material. Then, the reaction mixture was quenched with a saturated aqueous
NH4Cl solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic phases
were dried over Na2SO4. The solvent was removed under vacuum at room temperature. The
crude product was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to
afford the desired product 1a as a white solid (259 mg, 1.38 mmol, 58%).

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.30, KMnO4.

S4
 • 1H NMR (400 MHz, CDCl3): δ 7.44 – 7.35 (m, 2H, ArH), 7.32 – 7.23 (m, 3H,
ArH), 3.37 (s, 3H, NCH3), 2.06 (p, J = 2.9 Hz, 1H), 1.84 (d, J = 3.4 Hz, 2H), 0.80
(s, 2H).
• 13C NMR (101 MHz, CDCl3): δ 171.7, 145.1, 129.1, 126.8, 126.4, 37.9, 37.1, 16.9,
10.0.
The characterization data matched the reported values.1

N-(4-Methylphenyl)-N-methylbicyclo[1.1.0]butane-1-carboxamide (1b)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, 4-methyl-N-methylaniline (0.57 mL, 4.5 mmol, 0.90 equiv) and
triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom flask
and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution, crude
acyl chloride was added dropwise. Then, the reaction mixture was warmed to room temperature
and further stirred overnight. Next, the reaction mixture was quenched with a saturated aqueous
NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The combined organic layers
were dried over MgSO4, and the solvent was evaporated under reduced pressure to obtain the
compound 13 as a brown liquid (862 mg, 3.97 mmol, 79%). This crude compound was used in
the next step without further purification.

S5
Step II: A 50 mL round bottom flask was charged with ketone 13 (862 mg, 3.97 mmol, 1.00
equiv) and MeOH (12 mL, 0.33 M). The resulting solution was cooled to 0 °C, and NaBH4
(120 mg, 3.18 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the
reaction mixture was quenched with a saturated aqueous NH4Cl solution (20 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (25 mL) and
dried over Na2SO4. The solvent was removed under vacuum to afford the product 14 as brown
oil (860 mg, 3.92 mmol, 99%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 14 (860 mg, 3.92
mmol, 1.00 equiv) and dry DCM (12 mL, 0.33 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (1.35 g, 7.06 mmol, 1.80 equiv)
and Et3N (0.71 mL, 5.1 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 15 as a pale-yellow oil (1.02 g, 2.73 mmol,
70%). The crude product was used in the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 15
(1.02 g, 2.73 mmol, 1.00 equiv) and THF (6 mL, 0.5 M) under inert atmosphere. Then, the
solution was cooled to 0 °C and a solution of KOtBu (460 mg, 4.10 mmol, 1.50 equiv) in THF
(4 mL, 1.0 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for
30–60 mins. The reaction mixture was monitored by TLC to confirm the complete consumption
of the starting material. Then, the reaction mixture was quenched with a saturated aqueous
NH4Cl solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic phases
were dried over Na2SO4. The solvent was removed under vacuum at room temperature. The
crude product was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to
afford the desired product 1b as a pale yellow liquid (344 mg, 1.71 mmol, 63%). (See Spectra)

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.42, KMnO4.

• 1H NMR (400 MHz, CDCl3): δ 7.21 – 7.08 (m, 4H, ArH), 3.32 (s, 3H, NCH3), 2.35
(s, 3H, ArCH3), 2.01 (tt, J = 3.4, 2.4 Hz, 1H), 1.81 (d, J = 3.3 Hz, 2H), 0.77 (d, J =
2.4 Hz, 2H).
• 13C NMR (101 MHz, CDCl3): δ 171.7, 142.6, 136.2, 129.7, 126.7, 38.0, 37.0, 21.0,
16.5, 10.0.

S6
 • IR (Neat): υ 3045 (w), 2941 (m), 1638 (s), 1516 (s), 1431 (s), 1393 (s), 1267 (s),
1119 (s), 1043 (m), 727 (s).
• HRMS (ESI): calcd. for C13H16NO+ [M+H]+ 202.1232; found: 202.1231.
N-(4-Methoxyphenyl)-N-methylbicyclo[1.1.0]butane-1-carboxamide (1c)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, 4-methoxy-N-methylaniline (617 mg, 4.50 mmol, 0.900 equiv)
and triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom
flask and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution,
crude acyl chloride was added dropwise. Then, the reaction mixture was warmed to room
temperature and further stirred overnight. Next, the reaction mixture was quenched with a
saturated aqueous NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The
combined organic layers were dried over MgSO4, and the solvent was evaporated under
reduced pressure to obtain compound 16 as a brown liquid (854 mg, 3.66 mmol, 73%). This
crude compound was used in the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone 16 (854 mg, 3.66 mmol, 1.00
equiv) and MeOH (11 mL, 0.33 M). The resulting solution was cooled to 0 °C, and NaBH4
(111 mg, 2.93 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the

S7
reaction mixture was quenched with a saturated aqueous NH4Cl solution (20 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (25 mL) and
dried over Na2SO4. The solvent was removed under vacuum to afford the product 17 as brown
oil (852 mg, 3.62 mmol, 99%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 17 (852 mg, 3.62
mmol, 1.00 equiv) and dry DCM (12 mL, 0.33 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (1.24 g, 6.52 mmol, 1.80 equiv)
and Et3N (0.66 mL, 4.7 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 18 as a pale-yellow oil (965 mg, 2.48 mmol,
68%). The crude product was used in the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 18 (965
mg, 2.48 mmol, 1.00 equiv) and THF (6 mL, 0.4 M) under inert atmosphere. Then, the solution
was cooled to 0 °C and a solution of KOtBu (417 mg, 3.72 mmol, 1.50 equiv) in THF (4 mL,
0.9 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for 30 – 60
mins. The reaction mixture was monitored by TLC to confirm the complete consumption of
the starting material. Then, the reaction mixture was quenched with a saturated aqueous NH4Cl
solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic phases were dried
over Na2SO4. The solvent was removed under vacuum at room temperature. The crude product
was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to afford the desired
product 1c as a white solid (328 mg, 1.51 mmol, 61%). (See Spectra)

• Melting point: 46 – 54 ˚C.

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.31, KMnO4.
• 1H NMR (400 MHz, CDCl3): δ 7.20 – 7.11 (m, 2H), 6.92 – 6.83 (m, 2H), 3.81 (s,
3H, OCH3), 3.30 (s, 3H, NCH3), 2.06 – 1.97 (m, 1H), 1.82 – 1.75 (m, 2H), 0.79 –
0.74 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 171.7, 158.0, 138.0, 128.1, 114.3, 55.5, 38.2, 37.0,
16.3, 9.9.
• IR (Neat): υ 2952 (m), 2856 (w), 1632 (s), 1512 (s), 1463 (m), 1429 (s), 1396 (s)
1253 (s), 749 (s).

S8
 • HRMS (ESI): calcd. for C13H16NO2+ [M+H]+ 218.1181; found: 218.1185.

N-(4-Fluorophenyl)-N-methylbicyclo[1.1.0]butane-1-carboxamide (1d)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1.5 hours at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, 4-fluoro-N-methylaniline (0.49 mL, 4.5 mmol, 0.90 equiv) and
triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom flask
and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution, crude
acyl chloride was added dropwise. Then, the reaction mixture was warmed to room temperature
and further stirred overnight. Next, the reaction mixture was quenched with a saturated aqueous
NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The combined organic layers
were dried over MgSO4, and the solvent was evaporated under reduced pressure to obtain
compound 19 as a brown liquid (812 mg, 3.67 mmol, 73%). This crude compound was used in
the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone 19 (812 mg, 3.67 mmol, 1.00
equiv) and MeOH (11 mL, 0.33 M). The resulting solution was cooled to 0 °C, and NaBH4
(111 mg, 2.94 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the
reaction mixture was quenched with a saturated aqueous NH4Cl solution (20 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (25 mL) and

S9
dried over Na2SO4. The solvent was removed under vacuum to afford the product 20 as brown
oil (810 mg, 3.63 mmol, 99%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 20 (812 mg, 3.63
mmol, 1.00 equiv) and dry DCM (10 mL, 0.35 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (1.20 g, 6.55 mmol, 1.80 equiv)
and Et3N (0.66 mL, 4.7 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 21 as a pale-yellow oil (850 mg, 2.25 mmol,
62%). The crude product was used in the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 21 (850
mg, 2.25 mmol, 1.00 equiv) and THF (6 mL, 0.4 M) under inert atmosphere. Then, the solution
was cooled to 0 °C and a solution of KOtBu (380 mg, 3.38 mmol, 1.50 equiv) in THF (4 mL,
0.8 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for 4 hours.
The reaction mixture was monitored by TLC to confirm the complete consumption of the
starting material. Then, the reaction mixture was quenched with a saturated aqueous NH4Cl
solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic phases were dried
over Na2SO4. The solvent was removed under vacuum at room temperature. The crude product
was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to afford the desired
product 1d as a brown liquid (240 mg, 1.17 mmol, 52%). (See Spectra)

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.38, KMnO4.

• 1H NMR (400 MHz, CDCl3): δ 7.25 – 7.18 (m, 2H, ArH), 7.13 – 7.00 (m, 2H,
ArH), 3.32 (s, 3H, NCH3), 2.05 (p, J = 2.9 Hz, 1H), 1.82 (d, J = 3.3 Hz, 2H), 0.80
(d, J = 2.4 Hz, 2H).
• 13C NMR (101 MHz, CDCl3): δ 171.7, 160.8 (d, J = 246.6 Hz), 141.1, 128.5 (d, J
= 8.4 Hz), 116.0 (d, J = 22.7 Hz), 38.1, 37.1, 16.9, 9.8.
• 19F NMR (376 MHz, CDCl3): δ -115.22.
• IR (Neat): υ 2942 (m), 1641 (s), 1513 (s), 1439 (m), 1395 (m), 1228 (s), 1121 (m).
• HRMS (ESI): calcd. for C12H13FNO+ [M+H]+ 206.0976; found: 206.0972.

S10
N-(4-Chlorophenyl)-N-methylbicyclo[1.1.0]butane-1-carboxamide (1e)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, 4-chloro-N-methylaniline (637 mg, 4.5 mmol, 0.90 equiv) and
triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom flask
and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution, crude
acyl chloride was added dropwise. Then, the reaction mixture was warmed to room temperature
and further stirred overnight. Next, the reaction mixture was quenched with a saturated aqueous
NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The combined organic layers
were dried over MgSO4, and the solvent was evaporated under reduced pressure to obtain
compound 22 as a brown liquid (877 mg, 3.69 mmol, 74%). This crude compound was used in
the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone 22 (877 mg, 3.69 mmol, 1.00
equiv) and MeOH (12 mL, 0.30 M). The resulting solution was cooled to 0 °C, and NaBH4
(112 mg, 2.95 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the
reaction mixture was quenched with a saturated aqueous NH4Cl solution (20 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (25 mL) and
dried over Na2SO4. The solvent was removed under vacuum to afford the product 23 as light-

S11
yellow oil (809 mg, 3.38 mmol, 91%). The crude alcohol was used in the tosylation step without
further purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 23 (809 mg, 3.38
mmol, 1.00 equiv) and dry DCM (3.4 mL, 1.0 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (1.16 g, 6.07 mmol, 1.80 equiv)
and Et3N (0.61 mL, 4.7 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 24 as a pale-yellow oil (821 mg, 2.08 mmol,
62%). The crude product was used in the the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 24 (821
mg, 2.08 mmol, 1.00 equiv) and THF (10 mL, 0.20 M) under inert atmosphere. Then, the
solution was cooled to 0 °C and a solution of KOtBu (351 mg, 3.12 mmol, 1.50 equiv) in THF
(0.73 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for 30 –
60 mins. The reaction mixture was monitored by TLC to confirm the complete consumption of
the starting material. Then, the reaction mixture was quenched with a saturated aqueous NH4Cl
solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic phases were dried
over Na2SO4. The solvent was removed under vacuum at room temperature. The crude product
was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to afford the desired
product 1e as a white solid (234 mg, 1.51 mmol, 72%). (See Spectra)

• Melting point: 68 – 71˚C.

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.37, KMnO4.
• 1H NMR (400 MHz, CDCl3): δ 7.38 – 7.30 (m, 2H, ArH), 7.25 – 7.17 (m, 2H,
ArH), 3.33 (s, 3H, NCH3), 2.11 – 2.03 (m, 1H), 1.85 (d, J = 3.3 Hz, 2H), 0.84 (d, J
= 2.5 Hz, 2H).
• 13C NMR (101 MHz, CDCl3): δ 171.7, 143.7, 131.9, 129.3, 128.0, 37.8, 37.3, 17.4,
9.9.
• IR (Neat): υ 3068 (w), 2946 (w), 1646 (s), 1497 (s), 1440 (m), 1394 (m), 1120 (m).
• HRMS (ESI): calcd. for C12H13ClNO+ [M+H]+ 222.0681; found: 222.0679.

S12
N-Benzyl-N-phenylbicyclo[1.1.0]butane-1-carboxamide (1f)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, N-benzylaniline (825 mg, 4.50 mmol, 0.90 equiv) and
triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom flask
and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution, crude
acyl chloride was added dropwise. Then, the reaction mixture was warmed to room temperature
and further stirred overnight. Next, the reaction mixture was quenched with a saturated aqueous
NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The combined organic layers
were dried over MgSO4, and the solvent was evaporated under reduced pressure to obtain
compound 25 as a brown liquid (784 mg, 2.81 mmol, 56%). This crude compound was used in
the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone 25 (784 mg, 2.81 mmol, 1.00
equiv) and MeOH (8.5 mL, 0.33 M). The resulting solution was cooled to 0 °C, and NaBH4
(83.0 mg, 2.19 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the
reaction mixture was quenched with a saturated aqueous NH4Cl solution (20 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (25 mL) and
dried over Na2SO4. The solvent was removed under vacuum to afford the product 26 as brown

S13
oil (723 mg, 2.57 mmol, 92%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 26 (723 mg, 2.57
mmol, 1.00 equiv) and dry DCM (8.0 mL, 0.33 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (882 mg, 4.63 mmol, 1.80
equiv) and Et3N (0.47 mL, 3.3 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 27 as a pale-yellow oil (826 mg, 1.90 mmol,
74%). The crude product was used in the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 27 (826
mg, 1.90 mmol, 1.00 equiv) and THF (5 mL, 0.4 M) under inert atmosphere. Then, the solution
was cooled to 0 °C and a solution of KOtBu (319 mg, 2.84 mmol, 1.50 equiv) in THF (3 mL,
0.9 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for 30–60
mins. The reaction mixture was monitored by TLC to confirm the complete consumption of
the starting material. Then, the reaction mixture was quenched with a saturated aqueous NH4Cl
solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic phases were dried
over Na2SO4. The solvent was removed under vacuum at room temperature. The crude product
was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to afford the desired
product 1f as a white solid (386 mg, 1.47 mmol, 77%). (See Spectra)

• Melting point: 55 – 58 ˚C.

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.70, KMnO4.
• 1H NMR (400 MHz, CDCl3): δ 7.36 – 7.19 (m, 8H, ArH), 7.18 – 7.11 (m, 2H,
ArH), 5.00 (s, 2H, benzyl CH2), 2.12 (p, J = 3.1 Hz, 1H), 1.86 (d, J = 3.3 Hz, 2H),
0.81 (d, J = 2.4 Hz, 2H).
• 13C NMR (101 MHz, CDCl3): δ 171.8, 143.6, 137.6, 129.0, 128.4, 128.3, 127.8,
127.2, 126.6, 53.5, 37.2, 17.3, 10.2.
• IR (Neat): υ 2936 (m), 2879 (m), 1640 (s), 1602 (m), 1501 (m), 1431 (s), 1397 (s),
1297 (s), 1084 (m).
• HRMS (ESI): calcd. for C18H18NO+ [M+H]+ 264.1388; found: 264.1385.

S14
N-(2-((tert-Butyldimethylsilyl)oxy)ethyl)-N-phenylbicyclo[1.1.0]butane-1-carboxamide
(1g)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, N-(2-((tert-butyldimethylsilyl)oxy)ethyl)aniline (1.13 g, 4.50

mmol, 0.900 equiv) and triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50
mL round bottom flask and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C.
To this solution, crude acyl chloride was added dropwise. Then, the reaction mixture was
warmed to room temperature and further stirred overnight. Next, the reaction mixture was
quenched with a saturated aqueous NaHCO3 solution (20 mL) and extracted with DCM (3×30
mL). The combined organic layers were dried over MgSO4, and the solvent was evaporated
under reduced pressure to obtain compound 28 as a brown liquid (985 mg, 2.83 mmol, 57%).
This crude compound was used in the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone 28 (985 g, 2.83 mmol, 1.00
equiv) and MeOH (8.6 mL, 0.33 M). The resulting solution was cooled to 0 °C, and NaBH4
(86.0 mg, 2.27 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the
reaction mixture was quenched with a saturated aqueous NH4Cl solution (15 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (20 mL) and

S15
dried over Na2SO4. The solvent was removed under vacuum to afford the product 29 as brown
oil (951 mg, 2.72 mmol, 96%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 29 (713 mg, 2.72
mmol, 1.00 equiv) and dry DCM (8.0 mL, 0.33 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (934 mg, 4.90 mmol, 1.80
equiv), Et3N (0.49 mL, 3.5 mmol, 1.3 equiv), were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (20 mL). The organic
phases were extracted with DCM (3×30 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 30 as a pale-yellow oil (1.03 g, 2.72 mmol,
75%). The crude product was used in the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 30
(1.03 g, 2.04 mmol, 1.00 equiv) and THF (5 mL, 0.4 M) under inert atmosphere. Then, the
solution was cooled to 0 °C and a solution of KOtBu (344 mg, 3.07 mmol, 1.50 equiv) in THF
(3.5 mL, 0.9 M) prepared in an inert atmosphere was added dropwise and stirred vigorously
for 30–60 mins. The reaction mixture was monitored by TLC to confirm the complete
consumption of the starting material. Then, the reaction mixture was quenched with a saturated
aqueous NH4Cl solution (20 mL) and extracted with Et2O (3×30 mL). The combined organic
phases were dried over Na2SO4. The solvent was removed under vacuum at room temperature.
The crude product was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane)
to afford the desired product 1g as a yellow liquid (423 mg, 1.28 mmol, 62%). (See Spectra)

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.81, KMnO4.

• 1H NMR (400 MHz, CDCl3): δ 7.36 – 7.30 (m, 4H, ArH), 7.25 – 7.17 (m, 1H,
ArH), 3.91 – 3.77 (m, 4H, NCH2CH2OTBS), 2.10 – 1.99 (m, 1H), 1.83 – 1.78 (m,
2H)), 0.85 (s, 9H, SiC(CH3)3), 0.80 – 0.74 (m, 2H)), 0.02 (s, 6H, Si(CH3)2).
• 13C NMR (101 MHz, CDCl3): δ 171.8, 144.6, 128.8, 127.6, 126.2, 60.2, 52.9, 37.1,
25.8, 18.2, 17.4, 10.2, -5.4.
• IR (Neat): υ 2941 (m), 2868 (m), 1645 (s), 1602 (m), 1501 (m), 1408 (s), 1367 (m),
1096 (s).
• HRMS (ESI): calcd. for C19H29NO2SiNa+ [M+Na]+ 354.1865; found: 354.1862.

S16
N-Cyclohexyl-N-phenylbicyclo[1.1.0]butane-1-carboxamide (1h)

Step I: a) Following a slightly modified procedure,1 to a 50 mL round bottom flask under inert
condition, a solution of 3-oxocyclobutane-1-carboxylic acid (570 mg, 5.00 mmol, 1.00 equiv)
in dry dichloromethane (15 mL, 0.33 M) was prepared and cooled down to 0 °C. To this
solution, DMF (3 drops) and oxalyl chloride (0.64 mL, 7.5 mmol, 1.5 equiv) were added
dropwise and stirred for 2 hours. Further, the reaction mixture was stirred for 1 hour at room
temperature. Next, the solvent and remaining oxalyl chloride were evaporated under reduced
pressure to obtain the crude acid chloride, which was used in the next step without further
purification.

b) Under an inert condition, 4-methyl-N-methylaniline (789 mg, 4.50 mmol, 0.900 equiv) and
triethylamine (2.40 mL, 17.5 mmol, 3.50 equiv) were taken into a 50 mL round bottom flask
and dissolved in dry DCM (15 mL, 0.33 M) and cooled down to 0 °C. To this solution, crude
acyl chloride was added dropwise. Then, the reaction mixture was warmed to room temperature
and further stirred overnight. Next, the reaction mixture was quenched with a saturated aqueous
NaHCO3 solution (20 mL) and extracted with DCM (3×30 mL). The combined organic layers
were dried over MgSO4, and the solvent was evaporated under reduced pressure to obtain the
compound 31 as a brown liquid (744 mg, 2.74 mmol, 55%). This crude compound was used in
the next step without further purification.

Step II: A 50 mL round bottom flask was charged with ketone 31 (744 mg, 2.74 mmol, 1.00
equiv) and MeOH (8.5 mL, 0.33 M). The resulting solution was cooled to 0 °C, and NaBH4
(85.0 mg, 2.25 mmol, 0.800 equiv) was added portion wise. After 1 hour stirring at 0 °C, the
reaction mixture was quenched with a saturated aqueous NH4Cl solution (15 mL) and extracted
with DCM (3×10 mL). The combined organic phases were washed with brine (15 mL) and
dried over Na2SO4. The solvent was removed under vacuum to afford the product 32 as brown

S17
oil (723 mg, 2.57 mmol, 92%). The crude alcohol was used in the tosylation step without further
purification.

Step III: A 50 mL two-neck round bottom flask charged with crude alcohol 32 (723 mg, 2.57
mmol, 1.00 equiv) and dry DCM (8.0 mL, 0.33 M) under inert atmosphere. Then, the solution
was cooled to 0 °C. To this solution, 4-toluenesulfonyl chloride (882 mg, 4.63 mmol, 1.80
equiv) and Et3N (0.47 mL, 3.3 mmol, 1.3 equiv) were added. After overnight stirring at room
temperature, the reaction was quenched with saturated aqueous NH4Cl (15 mL). The organic
phases were extracted with DCM (3×20 mL) and dried over Na2SO4. The solvent was removed
using rotary evaporator to afford desired product 33 as a pale-yellow oil (826 mg, 1.90 mmol,
74%). The crude product was used for the next step without purification.

Step IV: A 50 mL two-neck round bottom flask was charged with the tosylated product 33 (826
mg, 1.90 mmol, 1.00 equiv) and THF (5 mL, 0.4 M) under inert atmosphere. Then, the solution
was cooled to 0 °C and a solution of KOtBu (314 mg, 2.84 mmol, 1.50 equiv) in THF (3 mL,
0.9 M) prepared in an inert atmosphere was added dropwise and stirred vigorously for 30 – 60
mins. The reaction mixture was monitored by TLC to confirm the complete consumption of
the starting material. Then, the reaction mixture was quenched with a saturated aqueous NH4Cl
solution (15 mL) and extracted with Et2O (3×20 mL). The combined organic phases were dried
over Na2SO4. The solvent was removed under vacuum at room temperature. The crude product
was purified by flash chromatography (silica, 1.5:8.5 v/v EtOAc:Hexane) to afford the desired
product 1h as a white solid (363 mg, 1.38 mmol, 73%). (See Spectra)

• Melting point: 70 – 81 ˚C.

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.70, KMnO4.
• 1H NMR (400 MHz, CDCl3): δ 7.42 – 7.27 (m, 3H, ArH), 7.18 – 7.10 (m, 2H,
ArH), 4.60 (tt, J = 12.1, 3.6 Hz, 1H, cyclohexyl CH), 1.96 (p, J = 2.9 Hz, 1H), 1.91
– 1.79 (m, 4H), 1.77 – 1.68 (m, 2H), 1.46 – 1.30 (m, 1H), 1.23 -1.05 (m, 2H), 1.10
– 0.83 (m, 2H), 0.92 (m, 1H), 0.64 – 0.59 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 170.9, 140.2, 130.7, 128.6, 127.4, 55.1, 36.6, 31.5,
25.8, 25.4, 15.1, 10.6.
• IR (Neat): υ 2946 (m), 2867 (m), 1637 (s), 1601 (m), 1498 (m), 1456 (s), 1405 (s),
1254 (s), 710 (s).
• HRMS (ESI): calcd. for C17H22NO+ [M+H]+ 256.1701; found: 256.1703.

S18
2.2 Synthesis of radical precursors

S-Phenyl 4-fluorobenzenesulfonothioate (2b)

Step I: Following a modified procedure,2 to a 50 mL round bottom flask sodium sulphite (1.26
g, 10.0 mmol, 2.00 equiv), sodium bicarbonate (840 mg, 10.0 mmol, 2.00 equiv) and 4-
fluorobenzenesulfonyl chloride (973 mg, 5.00 mmol, 1.00 equiv) were dissolved in distilled
water (5 mL). The reaction mixture was stirred at 80˚ C for 4 hours. After cooling down to
room temperature, water was removed from the reaction mixture. Then, 10 mL of ethanol was
added to the reaction mixture and filtered it. The filtrate was then concentrated under reduced
pressure to obtain sodium 4-fluorobenzenesulfinate as a white solid crystalline powder (0.73
g, 4.0 mmol, 81%).

S19
Step II: To a 50 mL round bottom flask 1,2-diphenyldisulfane (327 mg, 1.50 mmol, 1.00
equiv), sodium 4-fluorobenzenesulfinate (656 mg, 3.60 mmol, 2.40 equiv), iodine (571 mg,
2.25 mmol, 1.50 equiv.) were mixed in DCM (7 mL, 0.2 M). The mixture was kept stirring at
room temperature for 10 hours and monitored the completion of reaction by TLC. Sodium
thiosulfate was added to the reaction mixture for removing excess iodine. The mixture was then
extracted using DCM (3×15 mL). The combined organic phases were washed with brine (3×15
mL), and dried using Na2SO4. The solvent was evaporated using reduced pressure. The
obtained crude product was purified by flash chromatography (silica, 1:10 v/v EtOAc:Hexane)
to afford the desired product 2b as a white solid (0.70 g, 2.6 mmol, 87%).

• TLC (EtOAc:Hexane, 2:8 v/v): Rf = 0.46, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.60 – 7.54 (m, 2H, ArH), 7.53 – 7.45 (m, 1H,
ArH), 7.37 (s, 2H, ArH), 7.36 (d, J = 2.6 Hz, 2H, ArH), 7.09 (t, J = 8.5 Hz, 2H,
ArH).
• 13C NMR (101 MHz, CDCl3): δ 136.6, 131.6, 130.4 (d, J = 9.8 Hz), 129.5, 116.0
(d, J = 22.8 Hz). **Three carbons were not resolved at 101 MHz.
• 19F NMR (376 MHz, CDCl3): δ -102.86.
The characterization data matched the reported values.2
Phenyl 4-fluorobenzenesulfonate (2c)

Following a modified procedure,3 p-fluorosulfonyl chloride (701 mg, 3.60 mmol, 1.00 equiv)
was added portion wise to a solution of phenol (282 mg, 3.00 mmol, 0.830 equiv) in pyridine
(5 mL, 0.6 M) in 25 mL round bottom flask. The mixture was then stirred at 45 °C for 15 hours.
After cooling the reaction mixture to room temperature, 5 mL of water was added and stirred
for more 3 hours. Further, this mixture was diluted with toluene (50 mL) and washed with 10%
aqueous HCl (2×10 mL), saturated aqueous NaHCO3 (20 mL), and brine. Then, the organic
layer was extracted and dried over Na2SO4. The reaction mixture was filtered further, and the
organic solvent was evaporated under reduced pressure. Further recrystallization was done
using EtOAc and hexane to obtain the product 2c as colourless crystal.
• TLC (EtOAc:Hexane, 2:8 v/v): Rf = 0.42, KMnO4.
• 1H NMR (400 MHz, CDCl3): δ 7.89 – 7.79 (m, 2H, ArH), 7.34 – 7.23 (m, 3H,
ArH), 7.20 (t, J = 8.3 Hz, 2H, ArH), 7.01 – 6.94 (m, 2H, ArH).

S20
 • 13C NMR (101 MHz, CDCl3): δ 166.0 (d, J = 257.3 Hz), 149.4, 131.4 (d, J = 9.6
Hz), 127.3, 116.5 (d, J = 22.9 Hz). **Three carbons were not resolved at 101 MHz.
• 19F NMR (376 MHz, CDCl3): δ -102.09.
The characterization data matched the reported values.3

2-((4-Fluorophenyl)sulfonyl)isoindoline-1,3-dione (2d)

Following a slightly modified procedure,4 a 100 mL round bottom flask was charged with 4-
fluorobenzenesulfonyl chloride (0.58 g, 3.0 mmol, 1.0 equiv), phthalimide (0.48 g, 3.3 mmol,
1.1 equiv) and acetonitrile (20 mL) was added. The mixture was cooled to 0 °C in an ice bath
for 30 minutes and triethylamine (0.84 mL, 6.0 mmol, 2.0 equiv) was added dropwise. The ice
bath was then removed, and the reaction mixture was stirred at room temperature for 3 hours
to form a white precipitate. The crude product was filtered, vacuum dried, and recrystallized
from acetonitrile to yield compound 2d as a white solid (0.56 g, 1.8 mmol, 61%).

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.3, UV.

• 1H NMR (600 MHz, CDCl3): δ 8.27 – 8.21 (m, 2H, ArH), 7.92 (dd, J = 5.6, 3.1
Hz, 2H, ArH), 7.82 (dd, J = 5.6, 3.0 Hz, 2H, ArH), 7.28 – 7.21 (m, 2H, ArH).
• 13C NMR (151 MHz, CDCl3): δ 166.4 (d, J = 258.3 Hz), 162.8, 135.6, 131.5 (d, J
= 9.8 Hz), 130.9, 124.7, 116.7 (d, J = 22.9 Hz). **One carbon was not resolved at
101 MHz.
• 19F NMR (565 MHz, CDCl3): δ -101.04.
The characterization data matched the reported values.4

N-(Diphenylmethylene)-4-fluorobenzenesulfonamide (2e)

Following a slightly modified procedure,5 a 100 mL round bottom flask was charged with 4-
fluorobenzenesulfonamide (1.8 g, 10 mmol, 1.0 equiv) and benzophenone (1.8 g, 10 mmol, 1.0
equiv). Then, the reaction vessel was evacuated and refilled with argon three times and the

S21
mixture was dissolved in dry DCE (40 mL). Titanium tetrachloride (0.66 mL, 6.0 mmol, 0.60
equiv) and triethylamine (2.8 mL, 20 mmol, 2.0 equiv) were added dropwise successively. The
reaction mixture was heated to a reflux for 12 hours before it was quenched with water (40 mL)
and the reaction mixture was extracted with DCM (3×50 mL). The combined organic layer was
washed with 40 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2e as a white solid (1.7 g, 5.0 mmol, 50%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.3, UV.

• 1H NMR (400 MHz, CDCl3): δ 8.02 – 7.93 (m, 2H, ArH), 7.65 – 7.40 (m, 10H, ArH),
7.18 (m, 2H, ArH).
• 13C NMR (151 MHz, CDCl3): δ 179.3, 165.1 (d, J = 254.5 Hz), 137.5 (d, J = 3.2 Hz),
130.1 (d, J = 9.3 Hz), 128.2, 116.0 (d, J = 22.6 Hz). ** Three carbons were not resolved
at 151 MHz.
• 19F NMR (377 MHz, CDCl3): δ -105.50.
The characterization data matched the reported values.5

N-(Diphenylmethylene)-benzenesulfonamide (2f)

Following a modified procedure,6 benzenesulfonyl chloride (0.46 mL, 3.6 mmol, 1.2 equiv)
was taken in a 25 mL round bottom flask and pyridine (1.0 mL) was added. Then,
benzophenone imine (0.50 mL, 3.0 mmol, 1.0 equiv) was added dropwise and the reaction
mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched with 1N
HCl (20 mL) and extracted with DCM (3×30 mL). The organic phases were combined and
washed with 20 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2f as a white solid (0.77 g, 2.4 mmol, 80%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.25, UV.

• 1H NMR (600 MHz, CDCl3): δ 7.97 – 7.93 (m, 2H, ArH), 7.62 – 7.36 (m, 13H,
ArH).

S22
 • 13C NMR (151 MHz, CDCl3): δ 179.2, 141.5, 132.5, 128.8, 128.2, 127.3. ** Three
carbons were not resolved at 151 MHz.
The characterization data matched the reported values.5

N-(Diphenylmethylene)-4-methylbenzenesulfonamide (2g)

Following a slightly modified procedure,5 a 100 mL round bottom flask was charged with 4-
methylbenzenesulfonamide (1.7 g, 10 mmol, 1.0 equiv) and benzophenone (1.8 g, 10 mmol,
1.0 equiv). Then, the reaction vessel was evacuated and refilled with argon three times and the
mixture was dissolved in dry DCE (40 mL). Titanium tetrachloride (0.66 mL, 6.0 mmol, 0.60
equiv) and triethylamine (2.8 mL, 20 mmol, 2.0 equiv) were added dropwise successively. The
reaction mixture was heated to a reflux for 12 hours before it was quenched with water (40 mL)
and the reaction mixture was extracted with DCM (3×50 mL). The combined organic layers
were washed with 40 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2g as a white solid (1.8 g, 5.4 mmol, 54%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.25, UV.

• 1H NMR (600 MHz, CDCl3): δ 7.85 – 7.81 (m, 2H, ArH), 7.58 – 7.51 (m, 6H, ArH),
7.42 (s, 4H, ArH), 7.31 – 7.27 (m, 2H, ArH), 2.43 (s, 3H, ArCH3).
• 13C NMR (151 MHz, CDCl3): δ 178.8, 143.3, 138.6, 129.4, 128.1, 127.3, 21.6. **
Three carbons were not resolved at 151 MHz.
The characterization data matched the reported values.5

4-(tert-Butyl)-N-(diphenylmethylene)benzenesulfonamide (2h)

Following a modified procedure,6 a 50 mL round bottom flask was charged with 4-(tert-
butyl)benzenesulfonyl chloride (1.4 g, 6.0 mmol, 1.2 equiv) and was dissolved in pyridine (2.0
mL). Then, benzophenone imine (0.84 mL, 5.0 mmol, 1.0 equiv) was added dropwise and the

S23
reaction mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched
with 1N HCl (40 mL) and extracted with DCM (3×50 mL). The organic phases were combined
and washed with 40 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2h as a white solid (1.1 g, 2.9 mmol, 58%).
(See Spectra)

• Melting Point: 146 – 148 °C.

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.35, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.78 (d, J = 8.5 Hz, 2H, ArH), 7.60 – 7.24 (m, 12H,
ArH), 1.28 (s, 9H, C(CH3)3).
• 13C NMR (151 MHz, CDCl3): δ 178.7, 156.3, 138.3, 128.1, 127.2, 125.8, 35.1, 31.1.
** Three carbons were not resolved at 151 MHz.
• IR (Neat): υ 2962 (m), 1588 (m), 1556 (s), 1445 (m), 1322 (s), 1157 (s), 1110 (m),
1087 (m).
• HRMS (ESI): calcd. for C23H23NO2SNa+ [M+Na]+ 400.1347; found: 400.1348.

N-(Diphenylmethylene)-4-methoxybenzenesulfonamide (2i)

Following a modified procedure,6 a 50 mL round bottom flask was charged with 4-

methoxybenzenesulfonyl chloride (1.2 g, 6.0 mmol, 1.2 equiv) and was dissolved in pyridine
(2.0 mL). Then, benzophenone imine (0.84 mL, 5.0 mmol, 1.0 equiv) was added dropwise and
the reaction mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched
with 1N HCl (40 mL) and extracted with DCM (3×50 mL). The organic phases were combined
and washed with 40 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2i as a white solid (1.2 g, 3.5 mmol, 71%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.12, UV.

• 1H NMR (600 MHz, CDCl3): δ 7.88 – 7.84 (m, 2H, ArH), 7.56 – 7.51 (m, 5H, ArH),
7.45 – 7.40 (m, 5H, ArH), 6.97 – 6.92 (m, 2H, ArH), 3.87 (s, 3H, OCH3).

S24
 • 13C NMR (151 MHz, CDCl3): δ 178.4, 162.9, 133.2, 129.5, 128.1, 113.9, 55.6. **
Three carbons were not resolved at 151 MHz.
The characterization data matched the reported values.5

N-(4-(N-(Diphenylmethylene)sulfamoyl)phenyl)acetamide (2j)

Following a modified procedure,6 4-acetamidobenzenesulfonyl chloride (0.84 g, 3.6 mmol, 1.2

equiv) was taken in a 25 mL round bottom flask and pyridine (1.0 mL) was added. Then,
benzophenone imine (0.50 mL, 3.0 mmol, 1.0 equiv) was added dropwise and the reaction
mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched with 1N
HCl (20 mL) and extracted with DCM (3×30 mL). The organic phases were combined and
washed with 20 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2j as a white solid (0.74 g, 2.0 mmol, 65%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.1, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.92 – 7.84 (m, 2H, ArH, NHAc), 7.65 – 7.34 (m, 13H,
ArH), 2.22 (s, 3H, COCH3).
The characterization data matched the reported values.5

N-(Diphenylmethylene)-4-nitrobenzenesulfonamide (2k)

Following a modified procedure,6 a 25 mL round bottom flask was charged with 4-

nitrobenzenesulfonyl chloride (0.80 g, 3.6 mmol, 1.2 equiv) and was dissolved in pyridine (1.0
mL). Then, benzophenone imine (0.50 mL, 3.0 mmol, 1.0 equiv) was added dropwise and the
reaction mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched
with 1N HCl (20 mL) and extracted with DCM (3×30 mL). The organic phases were combined
and washed with 20 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9

S25
v/v EtOAc:Hexane mixture to yield compound 2k as a white solid (0.71 g, 1.9 mmol, 65%).
(See Spectra)

• Melting Point: 153 – 155 °C.

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.25, UV.
• 1H NMR (400 MHz, CDCl3): δ 8.39 – 8.32 (m, 2H, ArH), 8.20 – 8.12 (m, 2H, ArH),
7.64 – 7.54 (m, 6H, ArH), 7.46 (t, J = 7.7 Hz, 4H, ArH).
• 13C NMR (151 MHz, CDCl3): δ 180.9, 150.1, 147.2, 128.7, 128.5, 124.2. ** Three
carbons were not resolved at 151 MHz.
• IR (Neat): υ 3068 (w), 1583 (m), 1523 (s), 1443 (w), 1349 (m), 1309 (s), 1145 (s),
1086 (m).
• HRMS (ESI): calcd. for C19H15N2O4S+ [M+H]+ 367.0753; found: 367.0751.

N-(Diphenylmethylene)-thiophene-2-sulfonamide (2l)

Following a slightly modified procedure,5 a 50 mL round bottom flask was charged with
thiophene-2-sulfonamide (0.82 g, 5.0 mmol, 1.0 equiv) and benzophenone (0.91 g, 5.0 mmol,
1.0 equiv). Then, the reaction vessel was evacuated and refilled with argon three times and the
mixture was dissolved in dry DCE (20 mL). Titanium tetrachloride (0.33 mL, 3.0 mmol, 0.60
equiv) and triethylamine (1.4 mL, 10 mmol, 2.0 equiv) were added dropwise successively. The
reaction mixture was heated to a reflux for 12 hours before it was quenched with water (20 mL)
and the reaction mixture was extracted with DCM (3×30 mL). The combined organic layer was
washed with 20 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation to obtain the crude product. The crude product was purified through flash column
chromatography using 1:9 v/v EtOAc:Hexane mixture to yield compound 2l as a white solid
(0.68 g, 2.1 mmol, 41%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.15, UV.

• 1H NMR (600 MHz, CDCl3): δ 7.64 – 7.54 (m, 8H, ArH), 7.45 (m, 4H, ArH), 7.05
(dd, J = 5.0, 3.8 Hz, 1H, ArH).
• 13C NMR (151 MHz, CDCl3): δ 179.0, 142.4, 132.3, 130.0, 128.2, 127.0. ** Three
carbons were not resolved at 151 MHz.
The characterization data matched the reported values.5

S26
N-(Diphenylmethylene)-methanesulfonamide (2m)

Following a modified procedure,6 methanesulfonyl chloride (0.56 mL, 7.2 mmol, 1.2 equiv)
was taken in a 50 mL round bottom flask and pyridine (2.0 mL) was added. Then,
benzophenone imine (1.0 mL, 6.0 mmol, 1.0 equiv) was added dropwise and the reaction
mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched with 1N
HCl (40 mL) and extracted with DCM (3×50 mL). The organic phases were combined and
washed with 40 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2m as a white solid (1.2 g, 4.7 mmol, 79%).

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.12, UV.

• 1H NMR (600 MHz, CDCl3): δ 7.61 – 7.40 (m, 10H, ArH), 3.21 (s, 3H, CH3).
• 13C NMR (151 MHz, CDCl3): δ 179.6, 130.8, 128.2, 43.0. ** Two carbons were not
resolved at 151 MHz.
The characterization data matched the reported values.5

N-(Diphenylmethylene)-2-methylpropane-2-sulfonamide (2n)

Following a slightly modified procedure,5 a 50 mL round bottom flask was charged with 2-
methylpropane-2-sulfonamide (0.69 g, 5.0 mmol, 1.0 equiv) and benzophenone (0.91 g, 5.0
mmol, 1.0 equiv). Then, the reaction vessel was evacuated and refilled with argon three times
and the mixture was dissolved in dry DCE (20 mL). Titanium tetrachloride (0.33 mL, 3.0
mmol, 0.60 equiv) and triethylamine (1.4 mL, 10 mmol, 2.0 equiv) were added dropwise
successively. The reaction mixture was heated to a reflux for 12 hours before it was quenched
with water (20 mL) and the reaction mixture was extracted with DCM (3×30 mL). The
combined organic layers were washed with 20 mL brine, dried over MgSO4 and then the
solvent was removed via rotary evaporation. The crude product was purified through flash
column chromatography using 1:9 v/v EtOAc:Hexane mixture to yield compound 2n as a white
solid (0.67 g, 2.3 mmol, 45%).

S27
 • TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.3, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.75 – 7.38 (m, 10H, ArH), 1.56 (s, 9H, C(CH3)3).
• 13C NMR (151 MHz, CDCl3): δ 180.3, 138.1, 136.0, 133.3, 130.5, 128.5, 127.8, 59.3,
24.2. **Two carbons were not resolved at 151 MHz.
The characterization data matched the reported values.5

N-(Diphenylmethylene)piperidine-1-sulfonamide (2o)

Following a modified procedure,6 piperidine-1-sulfonyl chloride (0.34 mL, 2.4 mmol, 1.2
equiv) was taken in a 25 mL round bottom flask and pyridine (1.0 mL) was added. Then,
benzophenone imine (0.34 mL, 2.0 mmol, 1.0 equiv) was added dropwise and the reaction
mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched with 1N
HCl (20 mL) and extracted with DCM (3×30 mL). The organic phases were combined and
washed with 20 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2o as a white solid (0.30 g, 0.93 mmol, 46%).
(See Spectra)

• Melting Point: 128 – 132 °C.

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.32, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.79 – 7.33 (m, 10H, ArH), 3.35 – 3.30 (m, 4H,
CH2NCH2), 1.72 (p, J = 5.8 Hz, 4H), 1.64 – 1.58 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 178.9, 138.1, 136.1, 133.1, 130.5, 128.4, 127.9, 47.6,
25.1, 23.8.
• IR (Neat): υ 2939 (m), 2852 (w), 1589 (m), 1563 (s), 1446 (m), 1341 (s), 1275 (m),
1216 (w), 1164 (s), 1104 (w), 1054 (m).
• HRMS (ESI): calcd. for C18H20N2O2SNa+ [M+Na]+ 351.1143; found: 351.1145.

N-(Diphenylmethylene)morpholine-4-sulfonamide (2p)

S28
Following a modified procedure,6 morpholine-4-sulfonyl chloride (0.45 g, 2.4 mmol, 1.2
equiv) was taken in a 25 mL round bottom flask and pyridine (1.0 mL) was added. Then,
benzophenone imine (0.34 mL, 2.0 mmol, 1.0 equiv) was added dropwise and the reaction
mixture was heated at 65 °C for 12 hours. The reaction mixture was then quenched with 1N
HCl (20 mL) and extracted with DCM (3×30 mL). The organic phases were combined and
washed with 20 mL brine, dried over MgSO4 and then the solvent was removed via rotary
evaporation. The crude product was purified through flash column chromatography using 1:9
v/v EtOAc:Hexane mixture to yield compound 2p as a white solid (0.14 g, 0.42 mmol, 21%).
(See Spectra)

• Melting Point: 127 –130 °C.

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.12, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.79 – 7.35 (m, 10H, ArH), 3.93 – 3.76 (m, 4H,
CH2OCH2), 3.41 – 3.34 (m, 4H, CH2NCH2).
• 13C NMR (151 MHz, CDCl3): δ 180.3, 137.8, 135.9, 133.5, 130.7, 128.6, 128.0, 66.1,
46.8.
• IR (Neat): υ 2921 (w), 2857 (m), 1592 (m), 1562 (s), 1450 (m), 1351 (s), 1289 (m),
1265 (m), 1159 (s), 1114 (m), 1074 (m).
• HRMS (ESI): calcd. for C17H18N2O3SNa+ [M+Na]+ 353.0936; found: 353.0934.

Dimethyl (Z)-(((benzoyloxy)imino)(phenyl)methyl)phosphonate (2q)

Step I: Following a modified procedure,7 a 30 mL glass-vial was charged with benzoyl chloride
(2.32 mL, 20.0 mmol, 1.00 equiv) and cool down to 0 °C. Then, trimethyl phosphite (2.5 g, 20
mmol, 1.0 equiv) was added dropwise and stirred for 4 hours at room temperature. The obtained
crude product was used in the next step without any purification.

Step II: A 150 mL round bottom flask was charged with the crude product (4.3 g, 20 mmol,
1.0 equiv) and dissolved in ethanol (80 mL). To this solution, hydroxylamine hydrochloride
(1.53 g, 22.0 mmol, 1.10 equiv) and pyridine (1.95 mL, 24.0 mmol, 1.20 equiv) were added
successively. The reaction mixture was stirred for 15 hours at room temperature before it was

S29
quenched with aqueous 1N HCl (40 mL) and extracted with EtOAc (3×30 mL). The combined
organic layers were washed with brine, dried over MgSO4, and evaporated under vacuum to
obtain the crude hydroxyl imine product.

Step III: The crude hydroxyl imine (4.6 g, 20 mmol, 1.0 equiv) was dissolved in DCM (70
mL) in a 150 mL round bottom flask and cooled down to 0 °C. To this cold solution, Et3N (3.35
mL, 24.0 mmol, 1.20 equiv) and benzoyl chloride (2.44 mL, 21.0 mmol, 1.05 equiv) were
added dropwise and stirred for 12 hours. The solvent was evaporated under vacuum, and the
crude product was purified by flash column chromatography using 1:9 EtOAc/Hexane as eluent
to obtain the pure product 2q as white solid (E/Z mixture, 3.50 g, 10.5 mmol, 52%). (See
Spectra)

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.4, KMnO4.

• 1H NMR (400 MHz, CDCl3): δ 8.32 – 8.25 (m, 0.3 H, ArH, minor diastereomer), 7.86
– 7.80 (m, 0.7 H, ArH, major diastereomer), 7.76 – 7.34 (m, 4H, ArH, both
diastereomer), 3.94 (d, J = 11.2 Hz, 2H, P(OCH3)2, major diastereomer), 3.80 (d, J =
11.7 Hz, 1H, P(OCH3)2, minor diastereomer).
• 13C NMR (151 MHz, CDCl3): δ 163.0, 162.9, 160.5, 160.1, 159.2, 159.1, 133.8, 133.7,
132.1 (d, J = 17.8 Hz), 130.7, 130.6, 130.2, 129.7, 129.1, 129.0, 128.7, 128.6, 128.5,
128.4, 127.9, 54.6 (d, J = 6.6 Hz), 53.5 (q, J = 5.8 Hz).
• 31P NMR (162 MHz, CDCl3): δ 7.9 (major diastereomer), 3.5 (minor diastereomer).
• IR (Neat): 2957 (w), 2853 (w), 1756 (s), 1597 (w), 1489 (w), 1245 (s), 1180 (w), 1029
(s), 990 (s), 887 (w), 769 (w).
• HRMS (ESI): calcd. for C16H16NO5PNa+ [M+Na]+ 356.0664; found 356.0664.

S30
3. Procedures for photocatalyzed reactions
3.1 Optimization for sulfonylated spirocyclobutyl oxindole
3.1.1 Screening of radical precursors

An oven-dried 4 mL glass vial was charged with BCB 1a (19 mg, 0.10 mmol, 1.0 equiv),
radical precursor 2 (0.10 mmol, 1.0 equiv) and 4-CzIPN (1.6 mg, 2.0 mol%). Next, the vial
was closed with a screw-cap septum. The vial was degassed and refilled with argon using the
Schlenk-line technique (three times). Acetonitrile (1.0 mL, 0.1 M) was added to the mixture
and stirred for 24 hours under the irradiation of a 457 nm light source (Photocube). The solvent
was evaporated under reduced pressure. The yield and diastereomeric ratio (2:1) of the crude
product was calculated by 19F NMR using PhCF3 as an internal standard.

Radical Yield (%)

Entry
precursor 3a 4
1 2a 30 30
2 2b 32 0
3 2c 0 0
4 2d 0 0
5 2e 85 0

3.1.2 Screening of photocatalysts

S31
An oven-dried 4 mL glass vial was charged with BCB 1a (19 mg, 0.10 mmol, 1.0 equiv),
radical precursor 2e (34 mg, 0.10 mmol, 1.0 equiv) and photocatalyst (2.0 mol%). Next, the
vial was closed with a screw-cap septum. The vial was degassed and refilled with argon using
the Schlenk-line technique (three times). Acetonitrile (1.0 mL, 0.1 M) was added to the mixture
and stirred for 24 hours under the irradiation of a 457 nm light source (Photocube). The solvent
was evaporated under reduced pressure. The yield and diastereomeric ratio (2:1) of the crude
product was calculated by 19F NMR using PhCF3 as an internal standard.

Entry Photocatalyst Yield (%)

1 Ir(ppy)3 100
2 [Ir(dF(CF3)ppy)2(dtbpy)]PF6 70
3 [Ir(dFCF3ppy)2-(5,5′-dCF3bpy)]PF6 57
4 Ir(p-CF3-ppy)3 80
5 [Ru(bpy)3]Cl2 30

3.2 Optimization for trifluoromethylated spirocyclobutyl oxindole

3.2.1 Screening of stoichiometry of Togni II reagent

An oven-dried 4 mL glass vial was charged with the BCB 1a (19 mg, 0.10 mmol, 1.0 equiv),
Togni II reagent and Ir(ppy)3 (0.7 mg, 1 mol%). The vial was then closed with a screw-cap
septum, degassed, and refilled with Argon three times. Dry DCM (1 mL, 0.1 M) was added to
the mixture and stirred for 15 hours under the irradiation of a 457 nm light source (Photocube).
Then, the solvent was removed under reduced pressure. The yield and diastereomeric ratio
(1.6:1) of the crude product was calculated by 1H NMR using CH2Br2 as an internal standard.

Entry Togni II (equiv) Yield (%)

1 2.5 40
2 1.5 60
3 1.0 64

S32
3.2.1 Screening of solvent and concentration

An oven-dried 4 mL glass vial was charged with the BCB 1a (19 mg, 0.10 mmol, 1.0 equiv),
Togni II reagent (32 mg, 0.10 mmol, 1.0 equiv) and Ir(ppy)3 (0.7 mg, 1 mol%). The vial was
then closed with a screw-cap septum, degassed, and refilled with Argon three times. Then
solvent was added to the mixture and stirred for 15 hours under the irradiation of a 457 nm
light source (Photocube). Then, the solvent was removed under reduced pressure. The yield
and diastereomeric ratio (1.6:1) of the crude product was calculated by 1H NMR using CH2Br2
as an internal standard.

Entry Solvent (xx M) Yield (%)

1 DCM (0.1) 64
2 DCM (0.05) 69
3 MeCN (0.1) 74
4 MeCN (0.05) 78*

*Reaction was performed in 0.3 mmol scale.

3.3 General procedures

General procedure A
An oven-dried 30 mL glass vial was charged with BCB 1(a-h) (0.30 mmol, 1.0 equiv), radical
precursor 2(e-q) (0.36 mmol, 1.2 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%). Next, the vial was
closed with a screw-cap septum. The vial was degassed and refilled with argon using the
Schlenk-line technique (three times). Acetonitrile (3.0 mL, 0.1 M) was added to the mixture
and stirred for 12 to 24 hours under the irradiation of a 457 nm light source (Photocube). The
solvent was evaporated under reduced pressure. The crude product was purified by flash
column chromatography using EtOH:EtOAc:Hexane as eluent to obtain the pure
spirocyclobutyl oxindoles 3(a-s) and 5(a-d).

General procedure B
An oven-dried 30 mL glass vial was charged with BCB 1 (0.30 mmol, 1.0 equiv), Togni II
reagent (96 mg, 0.30 mmol, 3.0 equiv) and Ir(ppy)3 (2.0 mg, 1.0 mol%). Next, the vial was

S33
closed with a screw-cap septum. The vial was degassed and refilled with argon using the
Schlenk-line technique (three times). Acetonitrile (0.05 M) was added to the mixture and stirred
for 15 hours under the irradiation of a 457 nm light source (Photocube). The solvent was
evaporated under reduced pressure. The crude product was purified by flash column
chromatography using EtOH:EtOAc:Hexane as eluent to obtain the pure spirocyclobutyl
oxindoles 6(a-d).

4. Characterization data for the new compounds

3-((4-Fluorophenyl)sulfonyl)-1'-methylspiro[cyclobutane-1,3'-indolin]-2'-one (3a)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), Radical precursor
2e (122 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3a as a white solid (93 mg, 0.27 mmol, 90%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• Melting Point: 205 – 207 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.28, UV.
• 1H NMR (400 MHz, CDCl3): δ 8.03 – 7.94 (m, 2H, ArH), 7.37 (dd, J = 7.5, 1.2 Hz,
1H, ArH), 7.33 – 7.27 (m, 3H, ArH), 7.08 (td, J = 7.6, 1.0 Hz, 1H, ArH), 6.81 (d, J =
7.7 Hz, 1H, ArH), 4.19 (tt, J = 10.0, 8.4 Hz, 1H, ArSO2CH), 3.15 (d, J = 6.9 Hz, 5H),
2.44 – 2.33 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 176.6, 167.4, 164.8, 143.2, 132.9 (d, J = 3.2 Hz),
132.1, 131.7 (d, J = 9.5 Hz), 128.8, 122.3 (d, J = 122.0 Hz), 116.8 (d, J = 22.8 Hz),
108.3, 52.7, 42.4, 32.8, 26.4.
• 19F NMR (376 MHz, CDCl3): δ -102.68.
• IR (Neat): υ 2921 (s), 2854 (m), 1708 (s), 1611 (w), 1462 (m), 1372 (m), 1142 (s),
1091 (m).
• HRMS (ESI): calcd. for C18H16FNO3SNa+ [M+Na]+ 368.0733; found: 368.0731.

Minor Diastereomer:

S34
 • Melting Point: 207 – 210 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.32, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.99 – 7.89 (m, 2H, ArH), 7.66 – 7.59 (m, 1H, ArH),
7.35 – 7.21 (m, 3H, ArH), 7.15 (t, J = 7.5 Hz, 1H, ArH), 6.80 (d, J = 7.7 Hz, 1H, ArH),
4.29 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.18 (s, 3H, NCH3), 3.04 – 2.94 (m, 2H), 2.69 –
2.59 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 179.5, 167.3, 164.7, 143.3, 133.9 (d, J = 3.3 Hz),
131.1 (d, J = 9.8 Hz), 128.9, 123.5 (d, J = 43.5 Hz), 116.8 (d, J = 22.7 Hz), 107.9, 51.3,
42.7, 32.0, 26.3. **One carbon was not resolved at 101 MHz.
• 19F NMR (376 MHz, CDCl3): δ -102.92.
• IR (Neat): υ 2921 (s), 2853 (m), 1702 (s), 1610 (w), 1464 (m), 1375 (m), 1143 (s),
1088 (m), 833 (w).
• HRMS (ESI): calcd. for C18H16FNO3SNa+ [M+Na]+ 368.0733; found: 368.0749.

1'-Methyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3b)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3b as a white solid (93 mg, 0.27 mmol, 91%, 2:1 dr, separable diastereomers). (See
Spectra)
Major Diastereomer:
• Melting Point: 209 – 210 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.25, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.87 – 7.79 (m, 2H, ArH), 7.42 – 7.33 (m, 3H, ArH),
7.32 – 7.22 (m, 1H, ArH), 7.06 (td, J = 7.6, 1.0 Hz, 1H, ArH), 6.80 (d, J = 7.8 Hz, 1H,
ArH), 4.17 (tt, J = 10.0, 8.3 Hz, 1H, ArSO2CH), 3.25 – 3.08 (m, 5H), 2.46 (s, 3H,
ArCH3), 2.37 – 2.29 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 176.6, 145.0, 143.1, 134.0, 132.2, 130.0, 128.7, 128.6,
122.8, 121.6, 108.2, 52.6, 42.4, 32.7, 26.4, 21.6.

S35
 • IR (Neat): υ 2922 (s), 2854 (m), 1705 (s), 1604 (m), 1461 (m), 1372 (w), 1142 (s),
1090 (m).
• HRMS (ESI): calcd. for C19H19NO3SNa+ [M+Na]+ 364.0983; found: 364.0999

Minor Diastereomer:
• Melting Point: 204 – 206 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.3, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.0 Hz, 2H, ArH), 7.63 (d, J = 7.3 Hz, 1H,
ArH), 7.37 (d, J = 8.0 Hz, 2H, ArH), 7.30 (t, J = 7.7 Hz, 1H, ArH), 7.14 (t, J = 7.5 Hz,
1H, ArH), 6.79 (d, J = 7.7 Hz, 1H, ArH), 4.27 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.17 (s,
3H, NCH3), 3.04 – 2.94 (m, 2H), 2.68 – 2.58 (m, 2H), 2.46 (s, 3H, ArCH3).
• 13C NMR (101 MHz, CDCl3): δ 179.7, 144.9, 143.2, 134.8, 131.4, 130.0, 128.8, 128.3,
123.7, 123.2, 107.9, 51.1, 42.7, 32.0, 26.3, 21.6.
• IR (Neat): υ 2920 (s), 2853 (m), 1706 (s), 1611 (w), 1463 (m), 1375 (m), 1145 (s),
1086 (m)
• HRMS (ESI): calcd. for C19H19NO3SNa+ [M+Na]+ 364.0983; found: 364.0980.

1',5'-Dimethyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3c)

Following the general procedure A, BCB 1b (60 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 3:7:50 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3c as a white solid (103 mg, 0.290 mmol, 97%, 2:1 dr, separable diastereomers).
(See Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.24, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.87 – 7.80 (m, 2H, ArH), 7.40 (d, J = 8.0 Hz, 2H,
ArH), 7.18 (d, J = 1.7 Hz, 1H, ArH), 7.07 (dd, J = 7.9, 1.7 Hz, 1H, ArH), 6.69 (d, J =
7.9 Hz, 1H, ArH), 4.17 (tt, J = 9.9, 8.3 Hz, 1H), 3.14 (d, J = 7.0 Hz, 5H), 2.46 (s, 3H,
ArCH3), 2.39 – 2.28 (m, 5H).

S36
 • 13C NMR (101 MHz, CDCl3): δ 176.6, 145.0, 140.8, 134.0, 132.4, 130.0, 128.8, 122.5,
107.9, 52.7, 42.5, 32.8, 26.4, 21.7, 21.1. **Two carbons were not resolved.
• IR (Neat): υ 2933 (s), 2864 (w), 1793 (m), 1606 (w), 1465 (s), 1382 (m), 1288 (w),
1166 (s).
• HRMS (ESI): calcd. for C20H21NO3SNa+ [M+Na]+ 378.1140; found: 378.1145.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.28, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.84 – 7.76 (m, 2H, ArH), 7.37 (d, J = 8.0 Hz, 3H,
ArH), 7.12 – 7.05 (m, 1H, ArH), 6.67 (d, J = 7.9 Hz, 1H, ArH), 4.27 (p, J = 8.8 Hz, 1H,
ArSO2CH), 3.14 (s, 3H, NCH3), 3.01 – 2.91 (m, 2H), 2.66 – 2.56 (m, 2H), 2.45 (s, 3H,
ArCH3), 2.38 (s, 3H, ArCH3).
• 13C NMR (101 MHz, CDCl3): δ 179.6, 145.0, 140.9, 134.8, 132.9, 131.4, 130.1, 129.0,
128.4, 124.5, 107.7, 51.2, 42.8, 32.1, 26.3, 21.7, 21.1.
• IR (Neat): υ 2900 (s), 2864 (s), 1705 (m), 1505 (m), 1466 (m), 1373 (m), 1153 (m).
• HRMS (ESI): calcd. for C20H22NO3S+ [M+H]+ 356.1320; found: 356.1325.

5'-Methoxy-1'-methyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3d)

Following the general procedure A, BCB 1c (65 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 3:7:50 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3d as a white solid (107 mg, 0.290 mmol, 97%, 2:1 dr, separable diastereomers).
(See Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.18, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.82 (d, J = 8.0 Hz, 2H, ArH), 7.39 (d, J = 8.0 Hz, 2H,
ArH), 6.97 (d, J = 2.5 Hz, 1H, ArH), 6.79 (dd, J = 8.5, 2.5 Hz, 1H, ArH), 6.69 (d, J =
8.5 Hz, 1H, ArH), 4.22 – 4.08 (m, 1H, ArSO2CH), 3.79 (s, 3H, OCH3), 3.19 – 3.06 (m,
5H, NCH3), 2.46 (s, 3H), 2.38 – 2.28 (m, 2H).

S37
 • 13C NMR (101 MHz, CDCl3): δ 176.3, 156.2, 145.1, 136.6, 133.9, 133.5, 130.0, 129.6,
128.7, 126.4, 112.2, 109.7, 108.4, 55.9, 52.6, 42.7, 32.7, 26.6, 21.7.
• IR (Neat): υ 2933 (s), 2865 (m), 1749 (w), 1604 (w), 1468 (m), 1384 (m), 1309 (w),
1158 (s).
• HRMS (ESI): calcd. for C20H21NO4SNa+ [M+Na]+ 394.1089; found: 394.1091.
Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.26, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.0 Hz, 2H, ArH), 7.37 (d, J = 8.0 Hz, 2H,
ArH), 7.22 (d, J = 2.6 Hz, 1H, ArH), 6.82 (dd, J = 8.4, 2.6 Hz, 1H, ArH), 6.68 (d, J =
8.4 Hz, 1H, ArH), 4.27 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.85 (s, 3H, OCH3), 3.14 (s, 3H,
NCH3), 3.00 – 2.90 (m, 2H), 2.69 – 2.59 (m, 2H), 2.46 (s, 3H, ArCH3).
• 13C NMR (151 MHz, CDCl3): δ 179.3, 156.7, 145.0, 136.7, 134.8, 132.6, 130.0, 128.3,
113.6, 110.7, 108.3, 56.0, 51.2, 43.2, 32.1, 26.3, 21.6.
• IR (Neat): υ 2934 (s), 2865 (s), 1706 (m), 1658 (m), 1603(m), 1503(m), 1467 (m),
1374 (m), 1296(w), 1150 (m).
• HRMS (ESI): calcd. for C20H22NO4S+ [M+H]+ 372.1270; found: 372.1276.

5'-Fluoro-1'-methyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3e)

Following the general procedure A, BCB 1d (62 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 3:7:50 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3e as a white solid (91 mg, 0.25 mmol, 84%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.19, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.0 Hz, 2H, ArH), 7.40 (d, J = 8.0 Hz, 2H,
ArH), 7.11 (dd, J = 7.8, 2.6 Hz, 1H, ArH), 6.98 (td, J = 8.8, 2.5 Hz, 1H, ArH), 6.72 (dd,

S38
 J = 8.6, 4.1 Hz, 1H, ArH), 4.19 – 4.05 (m, 1H, ArSO2CH), 3.26 – 3.14 (m, 5H), 2.47 (s,
3H, ArCH3), 2.40 – 2.30 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 176.3, 159.3 (d, J = 241.1 Hz), 145.1, 139.2, 134.1,
133.7 (d, J = 7.74 Hz), 130.1, 128.7, 114.7 (d, J = 23.2 Hz), 110.0 (d, J = 25.0 Hz),
108.7 (d, J = 8.1 Hz), 52.5, 42.9, 32.7, 26.5, 21.7.
• 19F NMR (376 MHz, CDCl3): δ -120.07.
• IR (Neat): υ 2923 (s), 2853 (w), 1704 (m), 1598 (w), 1494 (s), 1335 (m), 1287 (s),
1145 (s).
• HRMS (ESI): calcd. for C19H18FNO3SNa+ [M+Na]+ 382.0889; found: 382.0889.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.26, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.2 Hz, 2H, ArH), 7.41 – 7.33 (m, 3H,
ArH), 6.99 (td, J = 8.8, 2.6 Hz, 1H, ArH), 6.70 (dd, J = 8.5, 4.0 Hz, 1H, ArH), 4.24 (p,
J = 8.7 Hz, 1H, ArSO2CH), 3.17 (s, 3H, NCH3), 2.99 – 2.89 (m, 2H), 2.71 – 2.61 (m,
2H), 2.46 (s, 3H, ArCH3).
• 13C NMR (101 MHz, CDCl3): δ 179.3, 160.9, 145.1, 139.1, 134.6, 133.0 (d, J = 8.08
Hz), 130.1, 128.4, 115.0 (d, J = 23.5 Hz), 112.0 (d, J = 25.1 Hz), 108.4 (d, J = 8.0 Hz),
51.0, 43.0, 31.9, 26.4, 21.6.
• 19F NMR (376 MHz, CDCl3): δ -119.44.
• IR (Neat): υ 2922 (m), 2852 (w), 1706 (s), 1614 (w), 1494 (s), 1355 (m), 1280 (s),
1145 (s).
• HRMS (ESI): calcd. for C19H18FNO3SNa+ [M+Na]+ 382.0889; found: 382.0886.

5'-Chloro-1'-methyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3f)

Following the general procedure A, BCB 1e (66.5 mg, 0.300 mmol, 1.00 equiv), radical
precursor 2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred
under irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude
product was purified by flash chromatography using (silica, 3:7:50 v/v/v
EtOH:EtOAc:Hexane) to afford the product 3f as a white solid (98 mg, 0.26 mmol, 87%, 2:1
dr, separable diastereomers). (See Spectra)

S39
Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.23, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.85 – 7.76 (m, 3H, ArH), 7.39 (d, J = 8.0 Hz, 2H),
7.33 (d, J = 2.1 Hz, 1H), 7.31 – 7.21 (m, 1H, ArH), 6.73 (d, J = 8.3 Hz, 1H), 4.13 (tt, J
= 9.9, 8.4 Hz, 1H, ArSO2CH), 3.24 – 3.14 (m, 5H), 2.46 (s, 3H, ArCH3), 2.43 – 2.32
(m, 2H,).
• 13C NMR (101 MHz, CDCl3): δ 176.2, 145.2, 141.7, 134.0, 133.8, 130.1, 129.6, 128.6,
128.5, 128.0, 126.4, 122.3, 109.2, 52.3, 42.6, 32.5, 26.5, 21.5.
• IR (Neat): υ 2933 (s), 2864 (w), 1715 (m), 1603 (w), 1465 (m), 1371 (m), 1291 (w),
1156 (s).
• HRMS (ESI): calcd. for C19H18ClNO3SNa+ [M+Na]+ 398.0594; found: 398.0590.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.28, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.83 – 7.76 (m, 2H, ArH), 7.50 (d, J = 2.1 Hz, 1H,
ArH), 7.38 (d, J = 8.0 Hz, 2H, ArH), 7.29 – 7.22 (m, 1H, ArH), 6.70 (d, J = 8.2 Hz, 1H,
ArH), 4.24 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.15 (s, 3H, NCH3), 2.98 – 2.88 (m, 2H),
2.69 – 2.59 (m, 2H), 2.46 (s, 3H, ArCH3).
• 13C NMR (101 MHz, CDCl3): δ 179.1, 145.1, 141.7, 134.3, 132.9, 130.1, 128.7, 128.6,
128.4, 124.2, 108.8, 50.9, 42.7, 31.9, 26.4, 21.7.
• IR (Neat): υ 2934 (s), 2864 (w), 1715 (m), 1602 (m), 1465 (m), 1373 (m), 1285 (w),
1152 (s).
• HRMS (ESI): calcd. for C19H19ClNO3S+ [M+H]+ 376.0774; found: 376.0773.

1'-Benzyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3g)

Following the general procedure A, BCB 1f (79 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 3:7:50 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3g as a white solid (89 mg, 0.21 mmol, 71%, 2:1 dr, separable diastereomers). (See
Spectra)

S40
Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.26, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.0 Hz, 2H, ArH), 7.39 (m, 3H, ArH), 7.34
– 7.22 (m, 5H, ArH), 7.21 – 7.12 (m, 1H, ArH), 7.07 – 6.99 m, 1H, ArH), 6.71 (d, J =
7.8 Hz, 1H, ArH), 4.86 (s, 2H, PhCH2), 4.20 (p, J = 8.3 Hz, 1H, ArSO2CH), 3.26 (m,
2H), 2.47 (s, 3H, ArCH3), 2.44 – 2.36 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 176.7, 145.1, 142.2, 135.5, 134.0, 132.2, 128.71,
128.67, 128.5, 127.6, 127.3, 122.8, 121.7, 109.2, 52.6, 44.0, 42.4, 32.8, 21.7. **One
carbon was not resolved 101 MHz.
• IR (Neat): υ 2934 (s), 2864 (w), 1705 (m), 1603 (m), 1471 (m), 1384 (m), 1309 (w),
1151 (s).
• HRMS (ESI): calcd. for C25H23NO3SNa+ [M+Na]+ 440.1296; found: 440.1298.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.34, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.0 Hz, 2H, ArH), 7.86 – 7.79 (m, 1H,
ArH), 7.39 (d, J = 8.0 Hz, 2H, ArH), 7.36 – 7.24 (m, 5H, ArH), 7.24 – 7.16 (m, 1H,
ArH), 7.13 (t, J = 7.5 Hz, 1H, ArH), 6.71 (d, J = 7.7 Hz, 1H, ArH), 4.88 (s, 2H, PhCH2),
4.34 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.11 – 3.01 (m, 2H), 2.77 – 2.67 (m, 2H), 2.48 (s,
3H, ArCH3).
• 13C NMR (101 MHz, CDCl3): δ 179.9, 145.0, 142.3, 135.6, 134.8, 131.3, 130.1, 128.8,
128.7, 128.3, 127.8, 127.3, 123.9, 123.3, 108.9, 51.2, 43.8, 42.8, 32.3, 21.7.
• IR (Neat): υ 2933 (s), 2865 (w), 1722 (s), 1604 (s), 1471 (m), 1386 (m), 1307 (w),
1168 (s).
• HRMS (ESI): calcd. for C25H24NO3S+ [M+H]+ 418.1477; found: 418.1474.

1'-(2-((tert-Butyldimethylsilyl)oxy)ethyl)-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one
(3h)

Following the general procedure A, BCB 1g (99 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was

S41
purified by flash chromatography using (silica, 3:7:50 v/v EtOH:EtOAc:Hexane) to afford the
product 3h as a white solid (144 mg, 0.30 mmol, 99%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.46, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.0 Hz, 2H, ArH), 7.44 – 7.33 (m, 3H,
ArH), 7.29 – 7.21 (m, 1H, ArH), 7.08 – 7.00 (m, 1H, ArH), 6.97 (d, J = 7.8 Hz, 1H,
ArH), 4.19 (p, J = 8.3 Hz, 1H, ArSO2CH), 3.87 – 3.76 (m, 4H, NCH2CH2O), 3.25 –
3.15 (m, 2H), 2.48 (s, 3H, ArCH3), 2.41 – 2.31 (m, 2H), 0.77 (s, 9H, SiC(CH3)3), -0.11
(s, 6H, Si(CH3)2).
• 13C NMR (101 MHz, CDCl3): δ 176.8, 145.1, 143.3, 134.2, 132.1, 130.1, 128.7, 128.4,
122.6, 121.6, 109.6, 60.9, 52.7, 42.8, 42.4, 32.9, 25.8, 21.7, 18.2, -5.6.
• IR (Neat): υ 2937 (s), 2866 (w), 1720 (m), 1604 (m), 1472 (m), 1365 (m), 1291 (w),
1152 (s).
• HRMS (ESI): calcd. for C26H35NO4SSiNa+ [M+Na]+ 508.1954; found: 508.1954.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.40, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.83 – 7.76 (m, 2H, ArH), 7.59 (dd, J = 7.5, 1.3 Hz,
1H, ArH), 7.36 (d, J = 8.0 Hz, 2H, ArH), 7.31 – 7.21 (m, 1H, ArH), 7.14 – 7.06 (m, 1H,
ArH), 6.92 (d, J = 7.8 Hz, 1H, ArH), 4.26 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.85 – 3.74
(m, J = 3.1 Hz, 4H, NCH2CH2O), 3.03 – 2.93 (m, 2H), 2.67 – 2.57 (m, 2H), 2.45 (s, 3H,
ArCH3), 0.77 (s, 9H, SiC(CH3)3), -0.11 (s, 6H, Si(CH3)2).
• 13C NMR (101 MHz, CDCl3): δ 179.9, 145.0, 143.3, 134.9, 131.2, 130.1, 128.6, 128.3,
123.6, 123.0, 109.1, 60.8, 51.2, 42.6, 32.1, 25.8, 21.7, 18.2, -5.5. **One carbon was not
resolved at 101 MHz.
• IR (Neat): υ 2937 (s), 2866 (w), 1715 (m), 1604 (w), 1472 (m), 1365 (m), 1286 (w),
1152 (s).
• HRMS (ESI): calcd. for C26H35NO4SSiNa+ [M+Na]+ 508.1954; found: 508.1953.

S42
1'-Cyclohexyl-3-tosylspiro[cyclobutane-1,3'-indolin]-2'-one (3i)

Following the general procedure A, BCB 1h (77 mg, 0.30 mmol, 1.0 equiv), radical precursor
2g (121 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation for 24 h. The solvent was evaporated in vacuo and the crude product was purified
by flash chromatography using (silica, 3:7:50 v/v/v EtOH:EtOAc:Hexane) to afford the product
3i as a white solid (84 mg, 0.20 mmol, 68%, 2:1 dr, separable diastereomers). (See Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.36, UV.
• 1H NMR (400 MHz, CDCl3):) δ 7.87 – 7.79 (m, 2H, ArH), 7.43 – 7.33 (m, 3H, ArH),
7.25 – 7.18 (1H, ArH), 7.15 – 6.94 (m, 2H, ArH), 4.14 (m, 2H, ArSO2CH, NCH), 3.19
– 3.07 (m, 2H), 2.47 (s, 3H), 2.40 – 2.30 (m, 2H), 2.16 – 2.01 (m, 2H), 1.91 – 1.82 (m,
2H), 1.74 – 1.65 (m, 5H), 1.45 – 1.27 (m, 1H).
• 13C NMR (101 MHz, CDCl3): δ 176.5, 145.1, 142.3, 134.0, 132.9, 130.1, 128.9, 128.3,
122.2, 121.9, 110.2, 52.7, 52.4, 42.3, 29.1, 25.9, 25.4, 21.8. **One carbon was not
resolved at 101 MHz.
• IR (Neat): υ 2933 (s), 2864 (w), 1710 (m), 1616 (m), 1471 (s), 1382 (m), 1282 (w),
1181 (s).
• HRMS (ESI): calcd. for C24H27NO3SNa+ [M+Na]+ 432.1609; found: 432.1606.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 3:7:50 v/v/v): Rf = 0.45, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.83 – 7.75 (m, 2H, ArH), 7.66 – 7.57 (m, 1H, ArH),
7.43 – 7.33 (m, 2H, ArH), 7.25 – 7.22 (m, 1H, ArH), 7.14 – 7.06 (m, 1H, ArH), 7.02 –
6.96 (d, J = 7.9 Hz, 1H), 4.25 (p, J = 8.7 Hz, 1H, ArSO2CH), 4.18 – 4.00 (m, 1H, NCH),
3.01 – 2.91 (m, 2H), 2.66 – 2.56 (m, 2H), 2.45 (s, 3H), 2.19 – 2.01 (m, 2H), 1.88 (d, J
= 13.0 Hz, 2H), 1.75 – 1.67 (m, 3H), 1.45 – 1.31 (m, 3H).
• 13C NMR (101 MHz, CDCl3): δ 179.6, 144.9, 142.3, 134.9, 132.0, 130.0, 128.5, 128.3,
124.0, 122.6, 109.8, 52.2, 51.2, 42.6, 32.3, 29.1, 25.9, 25.4, 21.7.
• IR (Neat): υ 2937 (s), 2868 (w), 1708 (m), 1618 (m), 1472 (m), 1368 (m), 1287 (w),
1151 (s).

S43
 • HRMS (ESI): calcd. for C24H27NO3SNa+ [M+Na]+ 432.1609; found: 432.1606.

1'-Methyl-3-(phenylsulfonyl)spiro[cyclobutane-1,3'-indolin]-2'-one (3j)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2f (116 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3j as a white solid (60 mg, 0.18 mmol, 61%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.22, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.95 (dt, J = 8.6, 1.9 Hz, 2H, ArH), 7.73 – 7.66 (m,
1H, ArH), 7.60 (dd, J = 8.3, 6.9 Hz, 2H, ArH), 7.37 (dd, J = 7.4, 1.2 Hz, 1H, ArH), 7.32
– 7.23 (m, 1H, ArH), 7.06 (td, J = 7.6, 1.0 Hz, 1H, ArH), 6.80 (d, J = 7.7 Hz, 1H, ArH),
4.20 (tt, J = 9.9, 8.3 Hz, 1H, ArSO2CH), 3.23 – 3.11 (m, 5H), 2.41 – 2.30 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 176.6, 143.1, 137.0, 134.0, 132.2, 129.4, 128.7, 128.6,
122.8, 121.6, 108.2, 52.5, 42.4, 32.7, 26.4.
• IR (Neat): υ 2936 (s), 2869 (w), 1710 (m), 1623 (m), 1480 (m), 1356 (m), 1287 (w),
1159 (s), 874 (m), 752 (m).
• HRMS (ESI): calcd. for C18H17NO3SNa+ [M+Na]+ 350.0827; found: 350.0826.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.24, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.92 (dt, J = 7.3, 1.4 Hz, 2H, ArH), 7.72 – 7.64 (m,
1H, ArH), 7.64 – 7.54 (m, 3H, ArH), 7.30 (td, J = 7.7, 1.3 Hz, 1H, ArH), 7.14 (td, J =
7.6, 1.0 Hz, 1H, ArH), 6.79 (d, J = 7.7 Hz, 1H, ArH), 4.30 (p, J = 8.7 Hz, 1H, ArSO2CH),
3.17 (s, 3H, NCH3), 3.05 – 2.95 (m, 2H), 2.64 (ddd, J = 11.1, 8.7, 2.8 Hz, 2H).
• 13C NMR (101 MHz, CDCl3): δ 179.6, 143.2, 137.8, 133.9, 131.3, 129.4, 128.9, 128.2,
123.7, 123.2, 107.9, 51.1, 42.8, 32.0, 26.3.
• IR (Neat): υ 2923 (s), 2855 (w), 1694 (m), 1494 (m), 1398 (m), 1308 (m), 1146 (s).
• HRMS (ESI): calcd. for C18H17NO3SNa+ [M+Na]+ 350.0827; found: 350.0823.

S44
3-((4-(tert-Butyl)phenyl)sulfonyl)-1'-methylspiro[cyclobutane-1,3'-indolin]-2'-one (3k)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2h (136 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3k as a white solid (104 mg, 0.27 mmol, 90%, 2:1 dr, separable diastereomers).
(See Spectra)

Major Diastereomer:
• Melting Point: 210 – 212 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.23, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.90 – 7.83 (m, 2H, ArH), 7.63 – 7.56 (m, 2H, ArH),
7.36 (d, J = 7.4 Hz, 1H, ArH), 7.31 – 7.27 (m, 1H, ArH), 7.06 (t, J = 7.5 Hz, 1H, ArH),
6.81 (d, J = 7.8 Hz, 1H, ArH), 4.23 – 4.10 (m, 1H, ArSO2CH), 3.23 (td, J = 9.9, 2.8 Hz,
2H), 3.17 (s, 3H, NCH3), 2.41 – 2.31 (m, 2H), 1.36 (s, 9H).
• 13C NMR (101 MHz, CDCl3): δ 176.6, 157.9, 143.3, 134.3, 132.4, 128.6, 128.5, 126.4,
122.7, 121.7, 108.2, 52.7, 42.6, 35.3, 32.7, 31.1, 26.4.
• IR (Neat): υ 2924 (m), 2858 (m), 1709 (s), 1611 (w), 1467 (m), 1375 (w), 1313 (m),
1149 (s), 1087 (m).
• HRMS (ESI): calcd. for C22H25NO3SNa+ [M+Na]+ 406.1453; found: 406.1451.

Minor Diastereomer:
• Melting Point: 209 – 210 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.26, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.87 – 7.80 (m, 2H, ArH), 7.63 – 7.54 (m, 3H, ArH),
7.30 (td, J = 7.7, 1.2 Hz, 1H, ArH), 7.13 (td, J = 7.6, 1.0 Hz, 1H, ArH), 6.79 (d, J = 7.8
Hz, 1H, ArH), 4.28 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.17 (s, 3H, NCH3), 3.04 – 2.94 (m,
2H), 2.69 – 2.59 (m, 2H), 1.35 (s, 9H).
• 13C NMR (101 MHz, CDCl3): δ 179.7, 157.9, 143.2, 134.7, 131.4, 128.8, 128.2, 126.4,
123.7, 123.2, 107.9, 51.2, 42.7, 35.3, 32.1, 31.0, 26.3.

S45
 • IR (Neat): υ 2920 (s), 2854 (m), 1697 (m), 1614 (w), 1460 (m), 1375 (w), 1310 (w),
1152 (m), 1088 (w).
• HRMS (ESI): calcd. for C22H25NO3SNa+ [M+Na]+ 406.1453; found: 406.1452.

3-((4-Methoxyphenyl)sulfonyl)-1'-methylspiro[cyclobutane-1,3'-indolin]-2'-one (3l)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2i (127 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3l as a yellow solid (91 mg, 0.25 mmol, 85%, 2:1 dr, separable diastereomers).
(See Spectra)

Major Diastereomer:
• Melting Point: 220 – 225 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.2, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.92 – 7.84 (m, 2H, ArH), 7.37 (d, J = 7.4 Hz, 1H,
ArH), 7.28 (t, J = 7.6 Hz, 1H, ArH), 7.11 – 7.01 (m, 3H, ArH), 6.80 (s, 1H, ArH), 4.24
– 4.10 (m, 1H, ArSO2CH), 3.89 (s, 3H, OCH3), 3.22 – 3.03 (m, 5H), 2.41 – 2.31 (m,
2H).
• 13C NMR (101 MHz, CDCl3): δ 176.7, 164.0, 143.2, 132.3, 130.9, 128.6, 128.3, 122.8,
121.6, 114.6, 108.2, 55.7, 52.8, 42.4, 32.9, 26.4.
• IR (Neat): υ 2920 (s), 2852 (m), 1709 (s), 1598 (w), 1462 (m), 1376 (w), 1261 (m),
1141 (s), 1088 (m).
• HRMS (ESI): calcd. for C19H19NO4SNa+ [M+Na]+ 380.0932; found: 380.0928.

Minor Diastereomer:
• Melting Point: 215 – 217 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.25, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.87 – 7.82 (m, 2H, ArH), 7.63 (dd, J = 7.4, 1.2 Hz,
1H, ArH), 7.30 (td, J = 7.8, 1.2 Hz, 1H, ArH), 7.14 (td, J = 7.5, 1.0 Hz, 1H, ArH), 7.06
– 6.99 (m, 2H, ArH), 6.79 (d, J = 7.7 Hz, 1H, ArH), 4.26 (p, J = 8.8 Hz, 1H, ArSO2CH),
3.89 (s, 3H, OCH3), 3.17 (s, 3H, NCH3), 3.01 – 2.93 (m, 2H), 2.68 – 2.58 (m, 2H).

S46
 • 13C NMR (101 MHz, CDCl3): δ 179.7, 163.9, 143.2, 131.4, 130.4, 129.3, 128.8, 123.7,
123.2, 114.6, 107.9, 55.7, 51.3, 42.7, 32.1, 26.3.
• IR (Neat): υ 2920 (s), 2852 (m), 1708 (s), 1595 (m), 1464 (m), 1375 (w), 1262 (m),
1143 (s), 1088 (m).
• HRMS (ESI): calcd. for C19H19NO4SNa+ [M+Na]+ 380.0932; found: 380.0934.

N-(4-((1'-Methyl-2'-oxospiro[cyclobutane-1,3'-indolin]-3-yl)sulfonyl)phenyl)acetamide
(3m)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2j (136 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3m as a white solid (45 mg, 0.12 mmol, 39%, 2:1 dr, inseparable diastereomers).
(See Spectra)

• TLC (EtOH:EtOAc:Hexane, 1:3:10 v/v/v): Rf = 0.1, UV.

• 1H NMR (600 MHz, CDCl3): δ 8.44 (s, 0.6H, NH for major diastereomer), 8.26 (s,
0.4H, NH for minor diastereomer), 7.83 – 7.74 (m, 4H, ArH for both diastereomers),
7.59 (dd, J = 7.4, 1.2 Hz, 0.3H, ArH for minor diastereomer), 7.36 (dd, J = 7.4, 1.2 Hz,
0.7H, ArH for major diastereomer), 7.28 (tdd, J = 7.8, 4.3, 1.2 Hz, 1H, ArH for both
diastereomers), 7.12 (td, J = 7.6, 0.9 Hz, 0.4H, ArH for minor diastereomer), 7.07 (td,
J = 7.6, 1.0 Hz, 0.6H, ArH for major diastereomer), 6.79 (dd, J = 15.1, 7.8 Hz, 1H, ArH
for both diastereomers), 4.28 – 4.11 (m, 1H, ArSO2CH, for both diastereomers), 3.20 –
3.11 (m, 4.3H), 2.99 – 2.92 (m, 0.7H), 2.64 – 2.57 (m, 0.7H), 2.35 (ddt, J = 12.5, 8.5,
1.8 Hz, 1.3H), 2.21 (s, 1H, COCH3 for minor diastereomer), 2.20 (s, 2H, COCH3 for
major diastereomer).
• 13C NMR (151 MHz, CDCl3): δ 179.7, 176.9, 169.2, 169.1, 143.7, 143.5, 143.2, 143.1,
132.2, 131.9, 131.3, 131.1, 129.9, 129.5, 128.9, 128.7, 123.7, 123.3, 123.1, 121.7,
119.6, 119.5, 108.4, 107.9, 52.6, 51.2, 42.8, 42.5, 32.7, 32.0, 26.5, 26.3, 24.6. **One
carbon was not resolved at 101 MHz.

S47
 • IR (Neat): υ 3328 (w), 2925 (m), 2854 (w), 1700 (s), 1591 (m), 1469 (w), 1375 (m),
1315 (s), 1144 (s), 1089 (m).
• HRMS (ESI): calcd. for C20H20N2O4SNa+ [M+Na]+ 407.1041; found: 407.1043.

1'-Methyl-3-((4-nitrophenyl)sulfonyl)spiro[cyclobutane-1,3'-indolin]-2'-one (3n)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2k (132 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3n as a white solid (40 mg, 0.11 mmol, 36%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• Melting Point: 210 – 213 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.26, UV.
• 1H NMR (400 MHz, CDCl3): δ 8.50 – 8.42 (m, 2H, ArH), 8.22 – 8.13 (m, 2H, ArH),
7.36 (d, J = 7.4 Hz, 1H, ArH), 7.34 – 7.28 (m, 1H, ArH), 7.11 – 7.05 (m, 1H, ArH), 6.82
(d, J = 7.7 Hz, 1H, ArH), 4.30 – 4.16 (m, 1H, ArSO2CH), 3.25 – 3.10 (m, 5H), 2.47 –
2.37 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 176.4, 151.1, 143.3, 142.8, 131.8, 130.4, 129.0, 124.6,
123.0, 121.7, 108.4, 52.7, 42.5, 32.7, 26.5.
• IR (Neat): υ 2923 (s), 2855 (m), 1709 (s), 1610 (m), 1530 (s), 1466 (m), 1350 (s), 1305
(m), 1148 (s), 1088 (m).
• HRMS (ESI): calcd. for C18H16N2O5SNa+ [M+Na]+ 395.0678; found: 395.0678.

Minor Diastereomer:
• Melting Point: 207 – 212 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.3, UV.
• 1H NMR (400 MHz, CDCl3): δ 8.46 – 8.39 (m, 2H, ArH), 8.17 – 8.09 (m, 2H, ArH),
7.63 (d, J = 7.4 Hz, 1H, ArH), 7.37 – 7.28 (m, 1H, ArH), 7.17 (t, J = 7.5 Hz, 1H, ArH),
6.81 (d, J = 7.8 Hz, 1H, ArH), 4.36 (p, J = 8.7 Hz, 1H, ArSO2CH), 3.18 (s, 3H, NCH3),
3.08 – 2.98 (m, 2H), 2.71 – 2.61 (m, 2H).

S48
 • 13C NMR (101 MHz, CDCl3): δ 179.3, 151.0, 143.6, 143.2, 130.8, 129.7, 129.1, 124.6,
123.6, 123.3, 108.1, 51.2, 42.9, 31.9, 26.3.
• IR (Neat): υ 2922 (m), 2854 (m), 1706 (s), 1611 (m), 1531 (s), 1467 (m), 1350 (s),
1307 (m), 1149 (s), 1087 (m).
• HRMS (ESI): calcd. for C18H16N2O5SH+ [M+H]+ 373.0858; found: 373.0859.

1'-Methyl-3-(thiophen-2-ylsulfonyl)spiro[cyclobutane-1,3'-indolin]-2'-one (3o)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2l (118 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3o as a sticky white solid (79 mg, 0.24 mmol, 79%, 2:1 dr, separable
diastereomers). (See Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.2, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.80 – 7.74 (m, 2H), 7.38 (d, J = 7.4 Hz, 1H), 7.31 –
7.20 (m, 2H), 7.07 (q, J = 7.7 Hz, 1H), 6.80 (d, J = 7.7 Hz, 1H), 4.28 (p, J = 9.2 Hz,
1H), 3.22 – 3.13 (m, 5H), 2.43 (ddd, J = 12.6, 6.5, 2.3 Hz, 2H).
• 13C NMR (151 MHz, CDCl3): δ 176.7, 143.2, 137.3, 135.1, 134.8, 132.2, 128.7, 128.2,
122.9, 121.7, 108.3, 53.6, 42.2, 33.0, 26.4.
• IR (Neat): υ 2936 (w), 1704 (s), 1612 (m), 1469 (m), 1377 (m), 1311 (s), 1141 (s),
1095 (m).
• HRMS (ESI): calcd. for C16H15NO3S2Na+ [M+Na]+ 356.0391; found: 356.0391.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.27, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.73 (ddd, J = 11.6, 4.4, 1.3 Hz, 2H), 7.58 (d, J = 7.4
Hz, 1H), 7.35 – 7.28 (m, 1H), 7.19 (dd, J = 4.9, 3.7 Hz, 1H), 7.14 (t, J = 7.5 Hz, 1H),
6.79 (d, J = 7.7 Hz, 1H), 4.38 (p, J = 8.7 Hz, 1H), 3.18 (s, 3H, NCH3), 3.06 – 2.96 (m,
2H), 2.75 – 2.65 (m, 2H).

S49
 • 13C NMR (151 MHz, CDCl3): δ 179.6, 143.3, 138.4, 134.4, 134.3, 131.2, 128.9, 128.1,
123.7, 123.2, 107.9, 52.4, 42.6, 32.2, 26.3.
• IR (Neat): υ 2939 (w), 1702 (s), 1613 (m), 1469 (m), 1375 (m), 1312 (s), 1140 (s),
1089 (m).
• HRMS (ESI): calcd. for C16H15NO3S2Na+ [M+Na]+ 356.0391; found: 356.0393.

1'-Methyl-3-(methylsulfonyl)spiro[cyclobutane-1,3'-indolin]-2'-one (3p)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2m (93.4 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3p as a white solid (79 mg, 0.30 mmol, 99%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• Melting Point: 217 – 219 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.1, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.45 (d, J = 7.4 Hz, 1H, ArH), 7.33 (t, J = 7.7 Hz, 1H,
ArH), 7.14 (t, J = 7.5 Hz, 1H, ArH), 6.85 (d, J = 7.8 Hz, 1H, ArH), 4.13 (p, J = 9.3 Hz,
1H, MeSO2CH), 3.27 – 3.11 (m, 5H), 3.06 (s, 3H, RSO2CH3), 2.65 – 2.55 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 177.1, 143.3, 132.2, 128.9, 123.1, 121.8, 108.4, 51.4,
42.5, 37.2, 32.8, 26.5.
• IR (Neat): υ 2921 (s), 2853 (m), 1706 (s), 1612 (m), 1464 (m), 1377 (m), 1309 (m),
1134 (s), 1100 (w).
• HRMS (ESI): calcd. for C13H15NO3SNa+ [M+Na]+ 288.0670; found: 288.0672.

Minor Diastereomer:
• Melting Point: 194 – 196 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.15, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.61 (dd, J = 7.4, 1.3 Hz, 1H, ArH), 7.30 (td, J = 7.7,
1.2 Hz, 1H, ArH), 7.13 (td, J = 7.6, 1.0 Hz, 1H, ArH), 6.81 (d, J = 7.7 Hz, 1H, ArH),

S50
 4.28 (p, J = 8.7 Hz, 1H, MeSO2CH), 3.20 (s, 3H, NCH3), 3.03 – 2.93 (m, 2H), 2.87 (s,
3H, RSO2CH3), 2.81 – 2.71 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 179.6, 143.2, 131.1, 128.9, 123.8, 123.3, 107.9, 49.6,
42.9, 38.5, 31.4, 26.3.
• IR (Neat): υ 2923 (m), 2854 (w), 1702 (s), 1608 (m), 1465 (m), 1375 (m), 1301 (m),
1129 (s), 1088 (m).
• HRMS (ESI): calcd. for C13H15NO3SH+ [M+H]+ 266.0851; found: 266.0851.

3-(Tert-butylsulfonyl)-1'-methylspiro[cyclobutane-1,3'-indolin]-2'-one (3q)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2n (109 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 24 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3q as a white solid (90 mg, 0.29 mmol, 98%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• Melting Point: 170 – 171 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.18, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.47 (dd, J = 7.4, 1.3 Hz, 1H, ArH), 7.31 (td, J = 7.8,
1.2 Hz, 1H, ArH), 7.11 (td, J = 7.6, 1.1 Hz, 1H, ArH), 6.83 (d, J = 7.8 Hz, 1H, ArH),
4.27 (tt, J = 10.0, 8.2 Hz, 1H, RSO2CH), 3.35 (ddt, J = 11.9, 9.9, 2.0 Hz, 2H), 3.18 (s,
3H, NCH3), 2.48 – 2.37 (m, 2H), 1.42 (s, 9H).
• 13C NMR (101 MHz, CDCl3): δ 176.4, 143.3, 132.4, 128.7, 122.7, 121.5, 108.3, 59.1,
45.1, 43.8, 33.3, 26.4, 23.6.
• IR (Neat): υ 2938 (w), 1707 (s), 1612 (m), 1469 (m), 1376 (m), 1277 (s), 1112 (s).
• HRMS (ESI): calcd. for C16H21NO3SNa+ [M+Na]+ 330.1140; found: 330.1140.

Minor Diastereomer:
• Melting Point: 169 – 172 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.26, UV.

S51
 • 1H NMR (400 MHz, CDCl3): δ 7.67 – 7.60 (m, 1H, ArH), 7.33 – 7.24 (m, 1H, ArH),
7.12 (t, J = 7.5 Hz, 1H, ArH), 6.79 (d, J = 7.7 Hz, 1H, ArH), 4.41 (p, J = 8.8 Hz, 1H,
RSO2CH), 3.20 (s, 3H, NCH3), 3.10 – 3.00 (m, 2H), 2.79 – 2.69 (m, 2H), 1.41 (s, 9H).
• 13C NMR (101 MHz, CDCl3): δ 179.8, 143.1, 131.4, 128.8, 123.7, 123.2, 107.8, 59.1,
43.9, 43.7, 33.0, 26.3, 23.5.
• IR (Neat): υ 2922 (m), 2853 (w), 1708 (s), 1612 (m), 1472 (m), 1375 (m), 1265 (s),
1106 (s).
• HRMS (ESI): calcd. for C16H21NO3SNa+ [M+Na]+ 330.1140; found: 330.1143.

1'-Methyl-3-(piperidin-1-ylsulfonyl)spiro[cyclobutane-1,3'-indolin]-2'-one (3r)

Following the general procedure A, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), radical precursor
2o (118 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 48 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3r as a white solid (55 mg, 0.16 mmol, 55%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.20, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.43 (dd, J = 7.4, 1.2 Hz, 1H, ArH), 7.31 (td, J = 7.8,
1.2 Hz, 1H, ArH), 7.11 (td, J = 7.5, 1.0 Hz, 1H, ArH), 6.83 (d, J = 7.7 Hz, 1H, ArH),
4.16 (tt, J = 10.0, 8.5 Hz, 1H, RSO2CH), 3.45 – 3.38 (m, 4H, N(CH2)2), 3.19 (s, 3H,
NCH3), 3.13 (dd, J = 10.0, 2.7 Hz, 2H), 2.51 – 2.41 (m, 2H), 1.73 – 1.56 (m, 6H).
• 13C NMR (101 MHz, CDCl3): δ 177.0, 143.1, 132.5, 128.6, 122.8, 121.6, 108.2, 49.4,
47.4, 43.2, 33.7, 26.3, 26.0, 23.8.
• IR (Neat): υ 2936 (m), 2853 (w), 1707 (s), 1612 (m), 1468 (m), 1376 (m), 1333 (m),
1161 (m), 1138 (m), 1099 (m).
• HRMS (ESI): calcd. for C17H22N2O3SNa+ [M+Na]+ 357.1249; found: 357.1249.

Minor Diastereomer:
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.24, UV.

S52
 • 1H NMR (400 MHz, CDCl3): δ 7.62 (d, J = 7.3 Hz, 1H, ArH), 7.29 (td, J = 7.8, 1.4
Hz, 1H, ArH), 7.12 (t, J = 7.5 Hz, 1H, ArH), 6.79 (d, J = 7.7 Hz, 1H, ArH), 4.22 (p, J =
8.7 Hz, 1H, RSO2CH), 3.26 (t, J = 5.3 Hz, 4H, N(CH2)2), 3.19 (d, J = 1.0 Hz, 3H,
NCH3), 2.94 (ddd, J = 11.2, 8.6, 2.6 Hz, 2H), 2.80 – 2.70 (m, 2H), 1.60 (dt, J = 24.9,
5.2 Hz, 6H).
• 13C NMR (151 MHz, CDCl3): δ 179.9, 143.1, 131.5, 128.8, 123.7, 123.2, 107.8, 46.9,
46.1, 43.8, 33.6, 26.2, 25.7, 23.8.
• IR (Neat): υ 2937 (m), 2853 (w), 1705 (s), 1612 (m), 1467 (m), 1375 (m), 1323 (s),
1138 (s), 1048 (m).
• HRMS (ESI): calcd. for C17H22N2O3SNa+ [M+Na]+ 357.1249; found: 357.1244.

1'-Methyl-3-(morpholinosulfonyl)spiro[cyclobutane-1,3'-indolin]-2'-one (3s)

Following the general procedure A, BCB 1a (37 mg, 0.20 mmol, 1.0 equiv), radical precursor
2p (79 mg, 0.24 mmol, 1.2 equiv) and Ir(ppy)3 (2.6 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 48 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:3:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 3s as a white solid (55 mg, 0.16 mmol, 82%, 2:1 dr, separable diastereomers). (See
Spectra)

Major Diastereomer:
• Melting Point: 205 – 206 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.18, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.44 (dd, J = 7.4, 1.2 Hz, 1H, ArH), 7.32 (td, J = 7.8,
1.2 Hz, 1H, ArH), 7.13 (td, J = 7.5, 1.0 Hz, 1H, ArH), 6.84 (d, J = 7.8 Hz, 1H, ArH),
4.23 – 4.14 (m, 1H, RSO2CH), 3.82 – 3.77 (m, 4H, O(CH2)2), 3.47 – 3.42 (m, 4H,
N(CH2)2), 3.24 – 3.10 (m, 5H), 2.53 – 2.46 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 176.9, 143.2, 132.4, 128.8, 122.9, 121.7, 108.3, 66.8,
49.2, 46.6, 43.3, 33.8, 26.4.
• IR (Neat): υ 2920 (m), 2853 (w), 1710 (s), 1613 (m), 1468 (m), 1376 (m), 1316 (w),
1152 (m), 1112 (m), 1075 (w).
• HRMS (ESI): calcd. for C16H20N2O4SNa+ [M+Na]+ 359.1041; found: 359.1040.

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Minor Diastereomer:
• Melting Point: 200 – 202 °C.
• TLC (EtOH:EtOAc:Hexane, 1:3:12 v/v/v): Rf = 0.2, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.61 (dd, J = 7.4, 1.2 Hz, 1H, ArH), 7.35 – 7.26 (m,
1H, ArH), 7.14 (t, J = 7.5 Hz, 1H, ArH), 6.80 (d, J = 7.8 Hz, 1H, ArH), 4.27 (p, J = 8.7
Hz, 1H, RSO2CH), 3.78 – 3.71 (m, 4H, O(CH2)2), 3.30 (dd, J = 5.7, 3.7 Hz, 4H,
N(CH2)2), 3.20 (s, 3H, NCH3), 3.01 – 2.91 (m, 2H), 2.83 – 2.73 (m, 2H).
• 13C NMR (101 MHz, CDCl3): δ 179.7, 143.2, 131.2, 128.9, 123.7, 123.2, 107.9, 66.6,
46.1, 46.0, 44.0, 33.5, 26.3.
• IR (Neat): υ 2921 (s), 2853 (m), 1709 (s), 1611 (m), 1457 (m), 1376 (m), 1320 (s),
1141 (m), 1114 (m), 1078 (m).
• HRMS (ESI): calcd. for C16H21N2O4S+ [M+H]+ 337.1222; found: 337.1234.

Dimethyl (1'-methyl-2'-oxospiro[cyclobutane-1,3'-indolin]-3-yl)phosphonate (5a)

Following the general procedure A, BCB 1a (37 mg, 0.20 mmol, 1.0 equiv), radical precursor
2q (80 mg, 0.24 mmol, 1.2 equiv) and Ir(ppy)3 (2.6 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:2:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 5a as a colorless sticky liquid (30 mg, 0.10 mmol, 51%, 2:1 dr). Only one
diastereomer was isolated. (See Spectra)

• TLC (EtOH:Hexane, 3:7 v/v): Rf = 0.47, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.52 (d, J = 7.4 Hz, 1H, ArH), 7.34 – 7.26 (m, 1H,
ArH), 7.11 (tt, J = 7.5, 1.2 Hz, 1H, ArH), 6.81 (d, J = 7.8 Hz, 1H, ArH), 3.87 (d, J =
10.6 Hz, 6H, P(OCH3)2), 3.17 (s, 3H, NCH3), 3.14 – 2.92 (m, 3H), 2.45 – 2.32 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 177.7 (d, J = 4.7 Hz), 143.0, 133.5, 128.3 (d, J = 10.0
Hz), 122.8 (d, J = 13.7 Hz), 121.7, 108.0 (d, J = 4.8 Hz), 53.0 (q, J = 5.7 Hz), 45.6 (d,
J = 20.8 Hz), 31.9, 26.2 (d, J = 6.4 Hz), 24.6.
• 31P NMR (162 MHz, CDCl3): δ 30.50.
• IR (Neat): υ 2937 (w), 2851 (w), 1707 (s), 1611 (m), 1492 (m), 1306 (w), 1243 (m),
1027 (s0, 823 (m), 754 (m).

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 • HRMS (ESI): calcd. for C14H18NO4PNa+ [M+Na]+ 318.0871; found 318.0870.

Dimethyl (5'-chloro-1'-methyl-2'-oxospiro[cyclobutane-1,3'-indolin]-3-yl)phosphonate
(5b)

Following the general procedure A, BCB 1e (44.5 mg, 0.200 mmol, 1.00 equiv), radical
precursor 2q (80 mg, 0.24 mmol, 1.2 equiv) and Ir(ppy)3 (2.6 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:2:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 5b as a colorless sticky liquid (45 mg, 0.14 mmol, 68%, 2:1 dr, separable
distereomers). (See Spectra)

Major diastereomer:
• TLC (EtOH:Hexane, 3:7 v/v): Rf = 0.45, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.48 (d, J = 2.1 Hz, 1H, ArH), 7.31 – 7.21 (m, 1H,
ArH), 6.72 (d, J = 8.3 Hz, 1H, ArH), 3.86 (d, J = 10.5 Hz, 6H, P(OCH3)2), 3.15 (s, 3H,
NCH3), 3.14 – 2.95 (m, 3H), 2.44 – 2.32 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 177.1 (d, J = 4.4 Hz), 141.5, 135.0, 128.2 (d, J = 13.7
Hz), 128.1, 122.2 (t, J = 14.3 Hz), 108.9, 52.9 (q, J = 5.3 Hz), 45.7 (d, J = 21.0 Hz),
31.7, 26.3 (q, J = 5.4 Hz), 24.5.
• 31P NMR (243 MHz, CDCl3): δ 30.65.
• IR (Neat): υ 2948 (w), 2851 (w), 1710 (s), 1611 (w), 1488 (w), 1298 (w), 1243 (m),
1029 (s), 814 (m).
• HRMS (ESI): calcd. for C14H17ClNO4PNa+ [M+Na]+ 352.0481; found 352.0482.

Minor diastereomer:
• TLC (EtOH:Hexane, 3:7 v/v): Rf = 0.42, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.58 (d, J = 2.1 Hz, 1H, ArH), 7.23 (dd, J = 8.2, 2.1
Hz, 1H, ArH), 6.69 (d, J = 8.7, Hz, 1H, ArH), 3.80 (d, J = 10.7 Hz, 6H, P(OCH3)2),
3.30 – 3.18 (m, 1H), 3.16 (d, J = 2.5 Hz, 3H, NCH3), 2.81 – 2.61 (m, 4H).
• 13C NMR (151 MHz, CDCl3): δ 179.7, 141.6, 133.8, 128.4, 124.2, 108.6, 52.7 (d, J =
6.9 Hz), 45.5 (d, J = 17.4 Hz), 31.3 (d, J = 5.8 Hz), 26.3, 23.3, 22.2.
• 31P NMR (243 MHz, CDCl3): δ 30.46.
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 • IR (Neat): υ 2948 (w), 2851 (w), 1710 (s), 1611 (w), 1488 (m), 1350 (m), 1245 (m),
1092 (s), 815 (s), 761 (w).
• HRMS (ESI): calcd. for C14H17ClNO4PNa+ [M+Na]+ 352.0481; found 352.0479.

Dimethyl (1'-benzyl-2'-oxospiro[cyclobutane-1,3'-indolin]-3-yl)phosphonate (5c)

Following the general procedure A, BCB 1f (80 mg, 0.30 mmol, 1.0 equiv), radical precursor
2q (120 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was
purified by flash chromatography using (silica, 1:2:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 5c as a colorless sticky liquid (36 mg, 0.10 mmol, 32%, 2:1 dr). (See Spectra)

• TLC (EtOH:Hexane, 3:7 v/v): Rf = 0.48, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 7.2 Hz, 1H, ArH), 7.35 – 7.21 (m, 5H,
ArH), 7.15 (td, J = 7.7, 1.3 Hz, 1H, ArH), 7.07 (td, J = 7.5, 1.1 Hz, 1H, ArH), 6.68 (d,
J = 7.7 Hz, 1H, ArH), 4.88 (s, 2H, NCH2Ph), 3.81 (d, J = 10.6 Hz, 6H, P(OCH3)2), 3.32
(h, J = 9.7 Hz, 1H, P(O)CH), 2.90 – 2.67 (m, 4H).
• 13C NMR (151 MHz, CDCl3): δ 180.5, 142.1, 135.8, 132.2, 128.8, 128.4, 127.6, 127.3,
123.6, 123.0, 108.7, 52.7 (d, J = 6.8 Hz), 45.6 (d, J = 17.9 Hz), 43.7, 31.6 (d, J = 6.0
Hz), 22.9 (d, J = 150.2 Hz).
• 31P NMR (243 MHz, CDCl3): δ 33.68.
• IR (Neat): υ 2947 (w), 2851 (w), 1707 (s), 1611 (w), 1489 (w), 1462 (w), 1242 (m),
1032 (s), 819 (w), 755 (m).
• HRMS (ESI): calcd. for C20H22NO4PH+ [M+H]+ 372.1365; found 372.1362.

Dimethyl (1'-cyclohexyl-2'-oxospiro[cyclobutane-1,3'-indolin]-3-yl)phosphonate (5d)

Following the general procedure A, BCB 1h (77 mg, 0.30 mmol, 1.0 equiv), radical precursor
2q (120 mg, 0.360 mmol, 1.20 equiv) and Ir(ppy)3 (3.9 mg, 2.0 mol%) were stirred under
irradiation of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was

S56
purified by flash chromatography using (silica, 1:2:30 v/v/v EtOH:EtOAc:Hexane) to afford
the product 5d as a colorless sticky liquid (47 mg, 0.13 mmol, 43%, 2:1 dr, separable
diastereomers). (See Spectra)
Major diastereomer:
• TLC (EtOH:Hexane, 3:7 v/v): Rf = 0.46, UV.
• 1H NMR (400 MHz, CDCl3): δ 7.52 (dd, J = 7.5, 1.3 Hz, 1H, ArH), 7.23 (dd, J = 7.8,
1.3 Hz, 1H, ArH), 7.07 (t, J = 7.5 Hz, 1H, ArH), 7.01 (d, J = 7.9 Hz, 1H, ArH), 4.17 –
4.01 (m, 1H, NCH), 3.88 (d, J = 10.5 Hz, 6H, P(OCH3)2), 3.21 – 2.88 (m, 3H), 2.44 –
2.33 (m, 2H), 2.12 (m, 3H), 1.93 – 1.81 (m, 2H), 1.77 – 1.68 (m, 3H), 1.47 – 1.31 (m,
1H), 1.31 – 1.10 (m, 1H).
• 13C NMR (101 MHz, CDCl3): δ 177.6, 142.0, 134.0, 128.0, 122.2, 121.9, 109.9, 53.0
(d, J = 6.6 Hz), 52.4, 45.3 (d, J = 20.4 Hz), 32.0 (d, J = 6.0 Hz), 29.1, 26.0, 25.8, 24.2.
• 31P NMR (162 MHz, CDCl3): δ 30.52.
• IR (Neat): υ 2934 (m), 2855 (w), 1705 (s), 1647 (w), 1606 (w), 1461 (w), 1250 (m),
1030 (s), 816 (m), 753 (m).
• HRMS (ESI): calcd. for C19H27NO4P+ [M+H]+ 364.1678; found 364.1676.

Minor diastereomer:
• TLC (EtOH:Hexane, 3:7 v/v): Rf = 0.43, UV.
• 1H NMR (600 MHz, CDCl3): δ 7.60 (dd, J = 7.4, 1.3 Hz, 1H, ArH), 7.22 (td, J = 7.8,
1.4 Hz, 1H, ArH), 7.07 (td, J = 7.5, 0.9 Hz, 1H, ArH), 6.98 (d, J = 7.9 Hz, 1H, ArH),
4.20 – 4.06 (m, 1H, NCH), 3.80 (d, J = 10.6 Hz, 6H), 3.25 (m, 1H, P(O)CH), 2.79 –
2.70 (m, 2H), 2.70 – 2.61 (m, 2H), 2.20 – 2.04 (m, 2H), 1.89 (dt, J = 13.3, 3.3 Hz, 2H),
1.77 – 1.71 (m, 3H), 1.46 – 1.35 (m, 2H), 1.30 – 1.20 (m, 1H).
• 13C NMR (151 MHz, CDCl3): δ 180.2, 142.1, 132.8, 128.1, 123.8, 122.3, 109.6, 52.6
(d, J = 6.5 Hz), 52.1, 45.3 (d, J = 17.6 Hz), 31.6 (d, J = 6.2 Hz), 29.1, 26.0, 25.4, 23.3,
22.3.
• 31P NMR (243 MHz, CDCl3): δ 33.93.
• IR (Neat): 2934 (m), 2855 (w), 1703 (s), 1608 (w), 1462 (w), 1242 (m), 1109 (w), 1032
(s), 818 (w), 752 (w).
• HRMS (ESI): calcd. for C19H27NO4P+ [M+H]+ 364.1678; found 364.1677.

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1'-Methyl-3-(trifluoromethyl)spiro[cyclobutane-1,3'-indolin]-2'-one (6a)

Following the general procedure B, BCB 1a (56 mg, 0.30 mmol, 1.0 equiv), Togni II reagent
(95 mg, 0.30 mmol, 1.0 equiv) and Ir(ppy)3 (1.9 mg, 1.0 mol%) were stirred under irradiation
of 457 nm for 15 h. The solvent was evaporated in vacuo and the crude product was purified
by flash chromatography using (silica, 1:9 v/v EtOAc:Hexane) to afford the product 6a as a
white sticky solid (60 mg, 0.24 mmol, 78%, 1.6:1 dr, inseparable diastereomers). (See Spectra)

• TLC (EtOAc:Hexane, 1:9 v/v): Rf = 0.25, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.51 – 7.41 (m, 1H, ArH for both diastereomers), 7.34
– 7.27 (m, 1H, ArH for both diastereomers), 7.13 (t, J = 7.5 Hz, 1H, ArH for both
diastereomers), 6.82 (dd, J = 12.9, 7.8 Hz, 1H, ArH for both diastereomers), 3.59 – 3.30
(m, 1H, CF3CH for both diastereomers), 3.20 (d, J = 2.0 Hz, 3H, NCH3 for both
diastereomers), 2.94 (td, J = 10.0, 2.8 Hz, 1H), 2.70 – 2.47 (m, 2H), 2.39 – 2.29 (m,
1H).
• 13C NMR (151 MHz, CDCl3): δ 177.5, 143.2, 133.2, 128.7, 128.5, 126.4 (q, J = 276.0
Hz), 122.8, 121.7, 108.2, 107.9, 45.3, 44.7, 43.2, 32.7 (q, J = 31.8 Hz), 30.9 (d, J = 3.6
Hz), 30.8 (d, J = 3.6 Hz), 26.4, 26.2. **Six carbons were not resolved at 151 MHz.
• 19F NMR (376 MHz, CDCl3): δ -73.78 (for major diastereomer), -74.21 (for minor
diastereomer).
• IR (Neat): υ 2920 (s), 2853 (m), 1719 (m), 1614 (w), 1461 (m), 1375 (w), 1274 (w),
1159 (m), 1088 (w).
• HRMS (ESI): calcd. for C13H13F3NO+ [M+H]+ 256.0949; found: 256.0956.

5'-Methoxy-1'-methyl-3-(trifluoromethyl)spiro[cyclobutane-1,3'-indolin]-2'-one (6b)

Following the general procedure B, BCB 1c (33 mg, 0.15 mmol, 1.0 equiv), Togni II reagent
(24 mg, 0.15 mmol, 1.0 equiv) and Ir(ppy)3 (1.0 mg, 1.0 mol%) were stirred under irradiation
of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was purified

S58
by flash chromatography using (silica, 8:92 v/v EtOAc:Hexane) to afford the product 6b as a
yellow liquid (24 mg, 0.08 mmol, 56%, 2:1 dr, inseparable diastereomers). (See Spectra)

• TLC (EtOAc:Hexane, 1:5 v/v): Rf = 0.36, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.1 – 7.0 (m, 1H, ArH for both the diastereomers), 6.86
– 6.80 (m, 1H, ArH for both the diastereomers), 6.76 – 6.64 (m, 1H, ArH for both the
diastereomers), 3.89 – 3.78 (m, 3H, OCH3 for both the diastereomers), 3.57 – 3.25 (m,
1H, CF3CH for both the diastereomers), 3.18 – 3.13 (m, 3H, NCH3 for both the
diastereomers), 2.98 – 2.88 (m, 2H), 2.69 – 2.51 (m, 1H), 2.38 – 2.27 (m, 1H).
• 13C NMR (101 MHz, CDCl3): δ 179.8, 177.1, 156.4, 156.3, 136.8, 136.7, 134.4, 112.6,
112.0, 110.7, 109.8, 108.3, 55.9, 43.7, 43.6, 32.6 (q, J = 32.2 Hz), 30.9, 30.8, 29.7, 26.4,
26.3. **Five carbons were not resolved at 101 MHz.
• 19F NMR (376 MHz, CDCl3): δ -73.79 (major diastereomer), -74.21 (minor
diastereomer).
• IR (Neat): υ 2922 (w), 2852 (w), 1706 (s), 1600 (w), 1496 (m), 1466 (m), 1280 (m),
1154 (s), 1088 (m), 1033 (m).
• HRMS (ESI): calcd. for C14H15F3NO2+ [M+H]+ 286.1055; found: 286.1051.

1'-(2-((tert-Butyldimethylsilyl)oxy)ethyl)-3-(trifluoromethyl)spiro[cyclobutane-1,3'-
indolin]-2'-one (6c)

Following the general procedure B, BCB 1g (99 mg, 0.30 mmol, 1.5 equiv), Togni II reagent
(94 mg, 0.30 mmol, 1.0 equiv) and Ir(ppy)3 (2.0 mg, 1.0 mol%) were stirred under irradiation
of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was purified
by flash chromatography using (silica, 3:97 v/v EtOAc:Hexane) to afford the product 6c as a
yellow liquid (57 mg, 0.14 mmol, 48%, 2:1 dr, inseparable diastereomers). (See Spectra)

• TLC (EtOAc:Hexane, 1:4 v/v): Rf = 0.73, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.53 – 7.37 (m, 1H, ArH for both the diastereomers),
7.31 – 7.20 (m, 1H, ArH for both the diastereomers), 7.14 – 7.02 (m, 1H, ArH for both
the diastereomers), 7.00 – 6.88 (m, 1H, ArH for both the diastereomers), 3.89 – 3.76
(m, 4H, NCH2CH2O for both the diastereomers), 3.58 – 3.27 (m, 1H, CF3CH for both

S59
 the diastereomers), 3.01 – 2.89 (m, 2H), 2.69 – 2.53 (m, 1H), 2.38 – 2.27 (m, 1H), 0.81
– 0.71 (m, 9H), -0.10 (h, J = 2.9 Hz, 6H).
• 13C NMR (101 MHz, CDCl3): δ 180.3, 177.6, 143.3, 143.2, 132.9, 131.6, 128.4, 128.2,
122.8, 122.7, 122.5, 121.5, 109.4, 109.1, 60.7, 45.3, 44.7, 43.2, 42.7, 42.5, 32.5 (q, J =
30.3 Hz), 30.92, 30.89, 25.7, 18.14, 18.11, -5.59, -5.61. **Four carbons were not
resolved at 101 MHz.
• 19F NMR (376 MHz, CDCl3): δ -73.80 (major diastereomer), -74.21 (minor
diastereomer).
• IR (Neat): υ 2926 (s), 2857 (m), 1714 (s), 1613 (w), 1464 (m), 1355 (m), 1278 (m),
1156 (s).
• HRMS (ESI): calcd. for C20H28F3NO2SiNa+ [M+Na]+ 422.1739; found: 422.1737.

1'-Cyclohexyl-3-(trifluoromethyl)spiro[cyclobutane-1,3'-indolin]-2'-one (6d)

Following the general procedure B, BCB 1h (99 mg, 0.30 mmol, 1.5 equiv), Togni II reagent
(94 mg, 0.30 mmol, 1.0 equiv) and Ir(ppy)3 (2.0 mg, 1.0 mol%) were stirred under irradiation
of 457 nm for 12 h. The solvent was evaporated in vacuo and the crude product was purified
by flash chromatography using (silica, 3:97 v/v EtOAc:Hexane) to afford the product 6d as a
yellow liquid (57 mg, 0.14 mmol, 66%, 1.8:1 dr, inseparable diastereomers). (See Spectra)

• TLC (EtOAc:Hexane, 1:5 v/v): Rf = 0.62, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.50 – 7.39 (m, 1H, ArH for both the diastereomers),
7.31 – 7.20 (m, 1H, ArH for both the diastereomers), 7.12 – 6.95 (m, 2H, ArH for both
the diastereomers), 4.22 – 4.01 (m, 1H, NCH for both the diastereomers), 3.57 – 3.26
(m, 1H, CF3CH for both the diastereomers), 3.02 – 2.86 (m, 1H), 2.68 – 2.51 (m, 1H),
2.40 – 2.26 (m, 1H), 2.23 – 2.03 (m, 2H), 1.99 – 1.64 (m, 5H), 1.63 – 1.52 (m, 2H),
1.50 – 1.31 (m, 1H), 1.31 – 1.19 (m, 1H).
• 13C NMR (151 MHz, CDCl3): δ 180.0, 177.5, 142.4, 142.3, 133.7, 132.4, 128.3, 128.1,
126.5 (d, J = 276.3 Hz), 123.2, 122.3, 122.2, 121.9, 109.9, 109.8, 52.5, 52.2, 45.6, 44.9,
43.1, 43.0, 32.5 (q, J = 31.8 Hz), 31.02, 30.98, 29.1, 26.0, 25.5. **Three carbons were
not resolved at 151 MHz.

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 • 19F NMR (376 MHz, CDCl3): δ -73.81 (major diastereomer), -74.19 (minor
diastereomer).
• IR (Neat): υ 2928 (s), 2855 (m), 1715 (m), 1707 (s), 1612 (m), 1466 (m), 1362 (m),
1280 (m), 1155 (s).
• HRMS (ESI): calcd. for C18H21F3NO+ [M+H]+ 324.1575; found: 324.1575.

5. Procedures for large scale reaction and product modifications

5.1 Large scale reaction

An oven-dried 100 mL Schlenk tube was charged with BCB 1a (450 mg, 2.40 mmol, 1.00
equiv), radical precursor 2g (960 mg, 2.90 mmol, 1.20 equiv) and Ir(ppy)3 (23 mg, 1.5 mol%).
Next, the tube was closed with a screw-cap septum, degassed and refilled with argon using the
Schlenk-line technique (three times). Acetonitrile (25 mL) was added to the mixture and stirred
for 24 hours under the irradiation of a 440 nm light source (Kessil lamps). The solvent was
evaporated under reduced pressure. The crude product was purified by flash column
chromatography using EtOH:EtOAc:Hexane (1:2:30, v/v/v) as eluent to obtain the pure
spirocyclobutyl oxindoles 3b as white solid (580 mg, 1.77 mmol, 74%, 2:1 dr, separable
diastereomers).

5.2 Product modifications

1'-Methyl-3-tosylspiro[cyclobutane-1,3'-indoline] (7)

A flame dried 5 mL Schlenk tube was charged with the spiro-oxindole 3b (34 mg, 0.10 mmol,
1.0 equiv) and dissolved in THF (1 mL). Then, 1.0 M solution of BH3•THF (0.4 mL, 0.4 mmol,
4 .0 equiv) was added dropwise. The resulting reaction mixture was refluxed for 12 hours.
Then, the reaction mixture was cool down to room temperature and quenched with 2 mL MeOH

S61
and thesolvent was evaporated under vacuum. The crude product was purified by flash column
chromatography using 1:9 EtOAc/Hexane as eluent to obtain the pure product 7 as gummy
solid (25.0 mg, 0.078 mmol, 78%). *Only one diastereomer was isolated. (See Spectra)

• TLC (EtOAc:Hexane, 3:7 v/v): Rf = 0.42, UV.

• 1H NMR (400 MHz, CDCl3): δ 7.79 (dd, J = 8.5, 2.1 Hz, 2H, ArH), 7.36 (d, J = 8.0
Hz, 2H, ArH), 7.31 – 7.27 (m, 1H, ArH), 7.13 (td, J = 7.7, 1.3 Hz, 1H, ArH), 6.78 (td,
J = 7.4, 1.0 Hz, 1H, ArH), 6.47 (d, J = 7.8 Hz, 1H, ArH), 3.79 (p, J = 8.8 Hz, 1H,
ArSO2CH), 3.33 (s, 2H, NCH2), 2.94 – 2.83 (m, 2H), 2.73 (s, 3H, NCH3), 2.46 (s, 3H,
ArCH3), 2.41 – 2.30 (m, 2H).
• 13C NMR (151 MHz, CDCl3): δ 152.3, 144.7, 135.0, 134.8, 129.9, 129.7, 128.6, 128.4,
126.5, 123.0, 118.6, 107.3, 68.7, 51.9, 41.4, 35.8, 35.3, 21.6.
• IR (Neat): υ 2931 (w), 2858 (w), 1647 (w), 1607 (m), 1462 (m), 1358 (m), 1180 (m0,
1032 (s), 818 (w).
• HRMS (ESI): calcd. for C19H21NO2SNa+ [M+Na]+ 350.1191; found 350.1190.

1'-Methylspiro[cyclobutane-1,3'-indolin]-2'-one (8)

A 25 mL sealed round bottom flask was charged with the spiro-oxindole 3b (34 mg, 0.10 mmol,
1.0 equiv) and Mg turnings (100 mg, 4.00 mmol, 40.0 equiv). To this mixture, dry MeOH (7
mL) was added and refluxed for 24 hours. The reaction mixture was filtered and evaporated
under vacuum. The crude mixture was purified by flash column chromatography using 1:19
EtOAc/Hexane as eluent to obtain the pure product 8 as semi-solid (12.0 mg, 0.065 mmol,
65%).

• TLC (EtOAc:Hexane, 2:8 v/v): Rf = 0.36, KMnO4.

• 1H NMR (400 MHz, CDCl3): δ 7.54 – 7.48 (m, 1H, ArH), 7.30 – 7.22 (m, 1H, ArH),
7.10 (td, J = 7.5, 1.0 Hz, 1H, ArH), 6.78 (dd, J = 7.7, 0.9 Hz, 1H, ArH), 3.18 (s, 3H,
NCH3), 2.72 – 2.60 (m, 2H), 2.42 – 2.19 (m, 4H).
• 13C NMR (101 MHz, CDCl3): δ 180.2, 142.9, 134.4, 127.8, 122.5, 122.2, 107.6, 48.11,
31.2, 26.1, 16.8.
The characterization data matched the reported values.8

S62
6. Radical trapping and fluorescence quenching experiments
6.1 Radical trapping experiment

Following the general procedure A, BCB 1a (19 mg, 0.10 mmol, 1.0 equiv), radical precursor
2e (39 mg, 0.12 mmol, 1.2 equiv), TEMPO (32 mg, 0.20 mmol, 2.0 equiv) and Ir(ppy)3 (0.7
mg, 2.0 mol%) were stirred under irradiation of 457 nm for 24 h. The yield of the crude product
was calculated using 19F NMR using PhCF3 as internal standard. The TEMPO adduct 9 was
detected in HRMS.

S63
6.2 Fluorescence quenching experiment

Figure 1: Fluorescence quenching of Ir(ppy)3 with BCB 1a.

Figure 2: Fluorescence quenching of Ir(ppy)3 with radical precursor 2e.

S64
 Figure 3: Fluorescence quenching of Ir(ppy)3 with radical precursor 2q.

6.3 Cyclic Voltammetry experiments

Cyclic Voltammetry Test Conditions: A cyclic voltammograms using (i) Working electrode:
Glassy Carbon, (ii) Counter electrode: Platinum-wire, (iii) Reference electrode: Ag+/AgCl,
n
Electrolyte: 0.1 M Bu4PF6. Substrate concentration: 1.5 mM, Solvent: Acetonitrile.
Voltammograms were calibrated using ferrocene as an internal standard.

Figure 4: Cyclic voltammogram of radical precursor 2e.

S65
 Figure 5: Cyclic voltammogram of radical precursor 2c.

7. Crystallography Data
• Crystal structure and data of compound 3a (major diastereomer)

Identification Code SHELXL-2019/1

Empirical Formula C18H16FNO3S
Molecular Weight 345.38
Temperature 120K
Wavelength 0.71073 Å
Crystal system Orthorhombic
Space group P b c n (60)
Unit cell dimensions a = 15.3853(9); b = 9.7399(6); c =
21.7621(13)
Angles α = 90; β = 90; γ = 90
Volume 3261.1 (3) Å3
Z 8

S66
 Density (Calculated). 1.407 g/cm3
Absorption coefficient 0.225 mm-1
F (000) 1440
Theta range for data collection 2.293 to 26.447
Index ranges -19<=h<=19, -12<=k<=12, -27<=l<=27
Reflections collected 71216
Independent reflections 3364 [R(int) = 0.0752]
Completeness 99.8 %
Structure Refinement SHELXL-2019/1 (Sheldrick, 2019)
Data/ restraints/ parameters 3364 / 0/ 218
Goodness of fit on F2 1.037
Final R indices [1>2 sigma (1)] R1 = 0.0323; wR2 = 0.0768
R indices (all data) R1 = 0.0453; wR2 = 0.0834
Extinction coefficient n/a
Largest diff. peak and hole 0.282 and -0.388 e. Å

• Crystal structure and data of compound 3b (minor diastereomer)

Identification Code SHELXL-2019/1

Empirical Formula C19H19NO3S
Molecular Weight 341.41
Temperature 298 K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P 21/c (14)
Unit cell dimensions a = 10.9889(3); b = 5.5027(2); c =
27.9937(8)

S67
 Angles α = 90; β = 97.4880(10); γ = 90
Volume 1678.30(9) Å3
Z 4
Density (Calculated). 1.351 g/cm3
Absorption coefficient 0.210 mm-1
F (000) 720
Theta range for data collection 2.94 to 26.21
Index ranges -13<=h<=13, -6<=k<=6, -35<=l<=35
Reflections collected 38531
Independent reflections 3432 [R(int) = 0.0474]
Completeness 99.8 %
Structure Refinement SHELXL-2019/1 (Sheldrick, 2019)
Data/ restraints/ parameters 3432 / 0/ 219
Goodness of fit on F2 1.119
Final R indices [1>2 sigma (1)] R1 = 0.0508; wR2 = 0.1445
R indices (all data) R1 = 0.0565; wR2 = 0.1492
Extinction coefficient n/a
Largest diff. peak and hole 0.297 and -0.461 e. Å

8. DFT Calculations
All calculations were carried out with the DFT method using the Gaussian16 program.9 The
structures were optimized with solvent effects of acetonitrile by using the SMD model10 at the
UM06-2x/6-31G(d) level of theory.11 Harmonic analyses were performed at the same level of
theory to verify all the stationary points as minima or first-order saddle points, and to obtain
the thermodynamic contributions to enthalpy and free energy at 298 K and 1 atm pressure. The
connection of every TS to its respective reactant and product was verified by intrinsic reaction
coordinate (IRC) analysis.12 To obtain more accurate values, single point calculations were
performed at SMD(Acetonitrile)/UM06-2x/6-311++G(d,p) level. The Gibbs Free Energy
corrections obtained at 298 K and 1 atm were added to the calculated single-point energies.
The optimized structures were generated using CYLview software.13

S68
Figure 6: The free energy profile for sulfone radical A addition to BCB 1a comparing the cyclisation
and direct addition pathways (Note: Distances in Å)

The sulfone radical A was found to readily add to the strained C-C bond of the BCB 1a with
an activation free energy barrier of 13.0 kcal mol-1. When sulfonyl chloride B is used as the
radical precursor, the formed intermediate Int-1 can now take two possible competing
pathways: i) cyclisation and ii) chlorine atom abstraction. The transition state TS-3 (for major
diastereomer of the direct addition product 4b is found to be slightly more stabilized than the
cyclisation transition states TS-2a and TS-2b, which is in agreement with the experimental
results obtained. The direct addition product can be suppressed by replacing the sulfonyl
chloride with our radical precursor N-sulfonyl ketimines, as Int-1 can now only undergo radical
cyclisation with two diastereomeric transition states TS-2a and TS-2b which differ in energy
by 0.8 kcal mol-1 which is in good agreement with the observed diastereomeric ratio. The two
transition states lead to the corresponding diastereomeric intermediates Int-2a and Int-2b

S69
which can be easily oxidized to yield the two diastereomers of the product, which match the
expected structures predicted by our crystal structures.

Coordinates of the Optimized geometries

----------------------------------------------------------------------------------------------------------------
1a
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-594.9461543
Zero-point correction= 0.225723 (Hartree/Particle)
Thermal correction to Energy= 0.238367
Thermal correction to Enthalpy= 0.239311
Thermal correction to Gibbs Free Energy= 0.185132
Sum of electronic and zero-point Energies= -594.556134
Sum of electronic and thermal Energies= -594.543490
Sum of electronic and thermal Enthalpies= -594.542546
Sum of electronic and thermal Free Energies= -594.596725
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C 2.49395 -1.35487 0.97986
C 2.90976 -1.47184 -0.43867
C 1.05456 -1.72241 0.84904
C 1.65514 -0.72784 -0.09050
H 2.80303 -2.43214 -0.94558
H 3.75340 -0.86410 -0.75488
H 0.37850 -1.33618 1.60837
H 0.79120 -2.70692 0.45693
H 2.98080 -0.81350 1.77860
C 1.48416 0.73622 -0.22241
O 2.44276 1.46496 -0.46057
N 0.23468 1.26053 -0.00873
C 0.13713 2.71944 -0.00567
H 0.89182 3.13971 0.66114
H -0.85529 3.00673 0.34025

S70
 H 0.29741 3.12179 -1.01180
C -0.96911 0.49825 -0.06599
C -1.22479 -0.35252 -1.14378
C -2.40422 -1.09220 -1.18016
C -3.34622 -0.96590 -0.16061
C -3.09964 -0.09852 0.90294
C -1.91312 0.62768 0.95561
H -0.49732 -0.43200 -1.94637
H -2.59226 -1.75782 -2.01723
H -4.26826 -1.53780 -0.19567
H -1.70603 1.28961 1.79207
H -3.82749 0.00627 1.70189

----------------------------------------------------------------------------------------------------------------
A
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-588.3436777
Zero-point correction= 0.046153 (Hartree/Particle)
Thermal correction to Energy= 0.050782
Thermal correction to Enthalpy= 0.051726
Thermal correction to Gibbs Free Energy= 0.018090
Sum of electronic and zero-point Energies= -588.297525
Sum of electronic and thermal Energies= -588.292896
Sum of electronic and thermal Enthalpies= -588.291952
Sum of electronic and thermal Free Energies= -588.325588
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
S 0.19623 0.00002 -0.27946
C -1.57275 -0.00024 0.10191
H -2.00586 0.90188 -0.33026
H -1.65945 -0.00054 1.19157
H -2.00575 -0.90212 -0.33085
O 0.74774 1.28076 0.20808

S71
 O 0.74823 -1.28052 0.20810

----------------------------------------------------------------------------------------------------------------
B
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-1048.5397537
Zero-point correction= 0.049478 (Hartree/Particle)
Thermal correction to Energy= 0.055115
Thermal correction to Enthalpy= 0.056059
Thermal correction to Gibbs Free Energy= 0.019922
Sum of electronic and zero-point Energies= -1048.490275
Sum of electronic and thermal Energies= -1048.484639
Sum of electronic and thermal Enthalpies= -1048.483694
Sum of electronic and thermal Free Energies= -1048.519831
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C -1.01232 1.48214 0.00020
S -0.42222 -0.18909 -0.00000
H -0.65439 1.97759 -0.90318
H -0.65693 1.97629 0.90530
H -2.10383 1.40927 -0.00147
Cl 1.64330 0.12577 -0.00006
O -0.73058 -0.83571 1.25761
O -0.73086 -0.83537 -1.25772

----------------------------------------------------------------------------------------------------------------
TS-1
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 1 (-487.2111 cm-1)
Electronic energy: HF=-1183.1233581
Zero-point correction= 0.272098 (Hartree/Particle)
Thermal correction to Energy= 0.290316
Thermal correction to Enthalpy= 0.291260

S72
Thermal correction to Gibbs Free Energy= 0.222899
Sum of electronic and zero-point Energies= -1182.851260
Sum of electronic and thermal Energies= -1182.833042
Sum of electronic and thermal Enthalpies= -1182.832098
Sum of electronic and thermal Free Energies= -1182.900459
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C 1.48800 0.46696 0.15360
C 1.41009 0.99833 -1.25444
C 0.41179 -0.58333 0.02656
C 0.07995 0.68045 -0.67781
H 1.78686 0.31106 -2.01635
H 1.63897 2.04798 -1.41733
H -0.15929 -0.83850 0.91583
H 0.69506 -1.43813 -0.59482
H 1.55188 1.12726 1.01153
C -0.84087 1.74986 -0.22456
O -0.51960 2.93291 -0.30138
N -2.03429 1.36579 0.33002
C -2.86266 2.43468 0.88598
H -3.27844 3.05934 0.08783
H -2.25970 3.06298 1.54330
H -3.67874 1.98883 1.45373
C -2.62795 0.08648 0.11586
C -2.72906 -0.44572 -1.17130
C -3.30557 -1.69978 -1.35982
C -3.80785 -2.41343 -0.27358
C -3.72560 -1.86976 1.00820
C -3.13262 -0.62647 1.20639
H -2.35838 0.12533 -2.01776
H -3.37490 -2.11064 -2.36245
H -4.26409 -3.38682 -0.42458
H -3.04608 -0.20688 2.20488
H -4.11373 -2.41983 1.86005

S73
 H 5.65674 0.08614 -0.30301
C 4.68186 0.57646 -0.23457
H 4.37279 0.95597 -1.20985
H 4.70189 1.37549 0.50859
O 3.39706 -1.66861 -0.78387
S 3.49227 -0.66263 0.29771
O 3.90452 -1.11760 1.64574

----------------------------------------------------------------------------------------------------------------
Int-1
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-1183.164602
Zero-point correction= 0.274763 (Hartree/Particle)
Thermal correction to Energy= 0.292619
Thermal correction to Enthalpy= 0.293563
Thermal correction to Gibbs Free Energy= 0.226007
Sum of electronic and zero-point Energies= -1182.889839
Sum of electronic and thermal Energies= -1182.871983
Sum of electronic and thermal Enthalpies= -1182.871039
Sum of electronic and thermal Free Energies= -1182.938595
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C -1.91980 0.46353 -0.68438
C -1.48500 1.65832 0.20387
C -0.50851 -0.16708 -0.54423
C -0.08641 1.14253 0.06088
H -1.87316 1.59277 1.22931
H -1.68383 2.65695 -0.19346
H -0.01995 -0.47631 -1.47225
H -0.48220 -1.00354 0.16709
C 1.13376 1.92599 0.13548
O 1.07951 3.13858 0.36259
N 2.33386 1.30273 -0.13189

S74
 C 3.51889 2.15248 -0.18904
H 3.30648 3.03540 -0.79349
H 4.33558 1.58914 -0.64116
H 3.82045 2.47878 0.81334
C 2.51302 -0.10383 -0.00035
C 2.09692 -0.76930 1.15554
C 2.27278 -2.14712 1.26607
C 2.88724 -2.86106 0.23937
C 3.32285 -2.19180 -0.90464
C 3.13309 -0.81912 -1.02904
H 1.93975 -2.65907 2.16388
H 3.02982 -3.93338 0.33060
H 3.45228 -0.29350 -1.92485
H 3.80217 -2.74180 -1.70879
S -3.22979 -0.56786 -0.04392
H -2.18379 0.73801 -1.70742
O -3.42383 -1.69092 -0.97076
O -2.92514 -0.87168 1.36122
C -4.66711 0.47766 -0.09594
H -4.86223 0.76129 -1.13193
H -4.49063 1.35787 0.52573
H -5.50013 -0.10690 0.30292
H 1.63414 -0.20406 1.96025

----------------------------------------------------------------------------------------------------------------
TS-2a
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 1 (-514.7450 cm-1)
Electronic energy: HF=-1183.1383172
Zero-point correction= 0.273954 (Hartree/Particle)
Thermal correction to Energy= 0.290964
Thermal correction to Enthalpy= 0.291908
Thermal correction to Gibbs Free Energy= 0.227304
Sum of electronic and zero-point Energies= -1182.864363
Sum of electronic and thermal Energies= -1182.847353

S75
Sum of electronic and thermal Enthalpies= -1182.846409
Sum of electronic and thermal Free Energies= -1182.911014
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C 1.55655 -0.31414 0.37790
C 0.45097 -0.07312 -0.67429
C 0.95703 0.80382 1.26400
C -0.28519 0.69029 0.41443
H -0.03563 -0.96248 -1.08934
H 0.79141 0.58021 -1.48816
H 1.46523 1.76743 1.12194
H 0.87005 0.58881 2.33281
C -1.29058 1.76945 0.17512
O -1.03134 2.96224 0.15641
N -2.54881 1.24880 -0.05036
C -3.60186 2.03632 -0.66287
H -3.63138 1.88511 -1.74773
H -3.39969 3.08716 -0.45429
H -4.56597 1.75593 -0.23351
C -2.60646 -0.14817 0.08411
C -1.77683 -0.63996 1.13808
C -1.53627 -2.03251 1.18979
C -2.10626 -2.87863 0.24379
C -2.96715 -2.37594 -0.73638
C -3.20265 -0.99591 -0.83111
H -0.94198 -2.44011 2.00214
H -1.92078 -3.94742 0.29774
H -3.81028 -0.59127 -1.63539
H -3.43464 -3.04896 -1.44789
S 3.24181 -0.03010 -0.13778
C 3.54203 -1.30715 -1.33859
H 4.56604 -1.17533 -1.69730
H 2.83475 -1.19304 -2.16281
H 3.42971 -2.28062 -0.85730

S76
 H 1.51693 -1.30491 0.83732
O 4.11918 -0.24855 1.02048
O 3.30365 1.27042 -0.81942
H -1.69292 -0.05948 2.05518

----------------------------------------------------------------------------------------------------------------
TS-2b
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 1 (-499.1293 cm-1)
Electronic energy: HF=-1183.1377044
Zero-point correction= 0.274029 (Hartree/Particle)
Thermal correction to Energy= 0.290988
Thermal correction to Enthalpy= 0.291932
Thermal correction to Gibbs Free Energy= 0.227850
Sum of electronic and zero-point Energies= -1182.863676
Sum of electronic and thermal Energies= -1182.846717
Sum of electronic and thermal Enthalpies= -1182.845772
Sum of electronic and thermal Free Energies= -1182.909854
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C 1.68209 -0.93997 0.26247
C 0.42069 -0.25610 0.83925
C 0.93238 -1.26024 -1.05365
C -0.33776 -0.83466 -0.35063
H 0.47050 0.84117 0.80768
H 0.12071 -0.58181 1.83826
H 0.98429 -2.29943 -1.38593
H 1.20642 -0.59274 -1.88053
C -1.49736 -1.75587 -0.15299
O -1.42193 -2.97443 -0.12704
N -2.67113 -1.05193 0.02901
C -3.84892 -1.66533 0.61203
H -3.79657 -2.73795 0.42366
H -4.74616 -1.25420 0.14462

S77
 H -3.89336 -1.49259 1.69324
C -2.51364 0.33537 -0.12234
C -1.58462 0.67692 -1.15304
C -1.12927 2.01375 -1.21097
C -1.59500 2.95320 -0.29641
C -2.55386 2.60509 0.65955
C -3.00041 1.27882 0.76346
H -0.44688 2.31022 -2.00179
H -1.24550 3.97981 -0.35604
H -3.68609 0.98485 1.55285
H -2.93525 3.35373 1.34644
S 3.11863 0.10184 0.04087
H 2.00259 -1.82735 0.81213
O 4.16871 -0.69651 -0.60661
O 2.68735 1.34360 -0.61680
C 3.63156 0.49344 1.69818
H 3.90146 -0.43016 2.21379
H 2.81579 1.00581 2.21254
H 4.50000 1.15203 1.61597
H -1.56051 0.07497 -2.05965

----------------------------------------------------------------------------------------------------------------
TS-3
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 1 (-462.9766 cm-1)
Electronic energy: HF=-2231.6945923
Zero-point correction= 0.324762 (Hartree/Particle)
Thermal correction to Energy= 0.349673
Thermal correction to Enthalpy= 0.350617
Thermal correction to Gibbs Free Energy= 0.265668
Sum of electronic and zero-point Energies= -2231.369830
Sum of electronic and thermal Energies= -2231.344920
Sum of electronic and thermal Enthalpies= -2231.343976
Sum of electronic and thermal Free Energies= -2231.428924
......................................................................................................................................................

S78
 Cartesian Coordinates
......................................................................................................................................................
O 0.19081 0.92867 3.14682
H 1.40939 -1.70108 1.92595
H 4.34866 -2.27930 1.25909
H 2.49466 -0.27980 1.96677
C 1.71122 -0.79603 1.39566
C 4.51481 -2.28225 0.17963
C -0.00144 1.11668 1.94802
H -1.49427 2.52914 3.38859
H -0.96650 3.95658 2.45962
H 4.05143 -3.15350 -0.28729
H 5.58551 -2.25662 -0.03878
C 0.65056 0.19030 0.97849
C -1.48563 2.99314 2.40313
C 2.07467 -0.92481 -0.10161
N -0.81512 2.09736 1.46821
O 4.36791 0.35538 0.18236
H 1.67620 -1.81848 -0.58645
S 3.80778 -0.80821 -0.51878
H -2.51086 3.16141 2.06424
H 0.79298 3.66978 0.06573
C 1.26618 0.36209 -0.39535
C -0.94203 2.40577 0.07480
C -0.02222 3.26421 -0.52766
H 1.91046 1.25098 -0.41820
O 3.92889 -0.86353 -1.98131
H 0.61138 0.36382 -1.26910
C -2.00971 1.88695 -0.65828
C -0.14861 3.57392 -1.87999
H -2.72801 1.23575 -0.16853
H 0.57363 4.23264 -2.35224
C -2.13299 2.20152 -2.01003
C -1.20029 3.03863 -2.62234
H -2.95935 1.79361 -2.58439

S79
 H -1.29739 3.27890 -3.67672
H -2.62486 -1.36252 -2.25462
C -2.69009 -2.39418 -1.90564
H -3.53886 -2.91179 -2.36161
H -1.75963 -2.93662 -2.07809
O -4.15762 -1.52310 0.12893
S -2.99487 -2.36056 -0.14889
O -2.91150 -3.71288 0.39378
Cl -1.16057 -1.17918 0.53610

----------------------------------------------------------------------------------------------------------------
Int-2a
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-1183.1786237
Zero-point correction= 0.276329 (Hartree/Particle)
Thermal correction to Energy= 0.293046
Thermal correction to Enthalpy= 0.293991
Thermal correction to Gibbs Free Energy= 0.231049
Sum of electronic and zero-point Energies= -1182.902294
Sum of electronic and thermal Energies= -1182.885577
Sum of electronic and thermal Enthalpies= -1182.884633
Sum of electronic and thermal Free Energies= -1182.947575
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C -1.58762 -0.55981 0.14305
C -0.91982 0.28348 1.24517
C -0.50374 -0.09500 -0.84851
C 0.35451 0.31630 0.38358
H -0.84122 -0.16467 2.23802
H -1.36049 1.28427 1.30602
H -0.82819 0.78597 -1.41072
H -0.08379 -0.84774 -1.51795
C 1.07069 1.65040 0.21751

S80
 O 0.55801 2.75246 0.18658
N 2.41278 1.38880 0.02843
C 3.36980 2.39350 -0.38520
H 3.69154 2.21029 -1.41533
H 4.24150 2.37260 0.27392
H 2.88248 3.36655 -0.32191
C 2.68822 0.03355 0.10134
C 1.50856 -0.63696 0.74880
C 1.44762 -2.09611 0.42293
C 2.55961 -2.74093 -0.03599
C 3.75854 -2.04798 -0.36155
H 0.54317 -2.64724 0.66636
H 2.53055 -3.81839 -0.17635
S -3.26034 -0.13141 -0.31879
C -4.21673 -0.53510 1.12530
H -5.25704 -0.28752 0.89920
H -3.85996 0.06308 1.96660
H -4.11572 -1.60241 1.33174
H -1.57482 -1.63554 0.33519
O -3.67026 -1.00966 -1.42351
O -3.32798 1.32179 -0.52684
C 3.79155 -0.63166 -0.34844
H 4.62362 -2.60148 -0.70879
H 4.64577 -0.09258 -0.74794
H 1.63328 -0.52311 1.84566

----------------------------------------------------------------------------------------------------------------
Int-2b
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-1183.179861
Zero-point correction= 0.276182 (Hartree/Particle)
Thermal correction to Energy= 0.292948
Thermal correction to Enthalpy= 0.293892
Thermal correction to Gibbs Free Energy= 0.230660

S81
Sum of electronic and zero-point Energies= -1182.903679
Sum of electronic and thermal Energies= -1182.886913
Sum of electronic and thermal Enthalpies= -1182.885969
Sum of electronic and thermal Free Energies= -1182.949201
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
C 1.72004 -0.66376 0.00411
C 0.55908 -0.06807 0.82044
C 0.89231 -0.49261 -1.28564
C -0.36157 -0.34873 -0.40419
H 0.67809 1.00996 0.96687
H 0.31445 -0.55453 1.76653
H 0.91324 -1.32139 -1.99446
H 1.12004 0.45142 -1.79104
C -1.11362 -1.65629 -0.19051
O -0.63243 -2.77297 -0.13802
N -2.44420 -1.34990 0.00934
C -3.42378 -2.31553 0.46167
H -4.30552 -2.28275 -0.18334
H -3.72205 -2.09910 1.49245
H -2.96767 -3.30441 0.41296
C -2.67884 0.01279 -0.08416
C -1.48619 0.63397 -0.75430
C -1.35537 2.08787 -0.43295
C -2.43584 2.78153 0.02939
C -3.66043 2.13926 0.36635
C -3.75034 0.72468 0.37068
H -0.42265 2.59088 -0.67483
H -2.36070 3.85697 0.16814
H -4.61928 0.22518 0.78953
H -4.49959 2.73026 0.71558
S 3.25756 0.24661 0.01882
H 1.94696 -1.70491 0.24264
O 4.20031 -0.42534 -0.88619

S82
 O 2.95291 1.66415 -0.22623
C 3.84225 0.08036 1.68992
H 4.00833 -0.97724 1.90356
H 3.10148 0.50684 2.36982
H 4.78146 0.63513 1.75715
H -1.63075 0.52164 -1.84933

----------------------------------------------------------------------------------------------------------------
4a
----------------------------------------------------------------------------------------------------------------
Number of imaginary frequencies: 0
Electronic energy: HF=-1643.3886281
Zero-point correction= 0.279003 (Hartree/Particle)
Thermal correction to Energy= 0.297894
Thermal correction to Enthalpy= 0.298838
Thermal correction to Gibbs Free Energy= 0.229372
Sum of electronic and zero-point Energies= -1643.109625
Sum of electronic and thermal Energies= -1643.090735
Sum of electronic and thermal Enthalpies= -1643.089790
Sum of electronic and thermal Free Energies= -1643.159256
......................................................................................................................................................
Cartesian Coordinates
......................................................................................................................................................
O 0.66311 -2.85408 -0.95701
H -1.94191 -2.30764 0.78166
H -4.52545 -1.13677 -0.26952
H -1.73729 -1.59901 -0.85431
C -1.54983 -1.46340 0.21519
C -4.66324 -0.10179 0.05119
C 0.89768 -1.71890 -0.56540
H 2.23393 -2.20669 -2.69319
H 3.34994 -0.82223 -2.55122
H -4.88146 -0.04678 1.11946
H -5.46179 0.37109 -0.52623
C -0.07363 -1.07839 0.42877

S83
 C 2.83208 -1.61062 -2.00368
C -1.92661 -0.04206 0.67361
N 1.95252 -0.99082 -1.01338
O -2.84218 0.65684 -1.70449
H -2.20799 0.03258 1.72626
S -3.17428 0.81023 -0.28124
H 3.57085 -2.25815 -1.51876
H 1.76796 1.37794 -2.17398
C -0.48201 0.40936 0.37705
C 2.37164 0.25607 -0.44450
C 2.22151 1.42876 -1.18780
H -0.39445 0.77410 -0.65155
O -3.31257 2.16916 0.25815
H -0.00269 1.10130 1.06962
C 2.96366 0.29210 0.81657
C 2.63454 2.64368 -0.65085
H 3.10643 -0.63198 1.36747
H 2.50873 3.55671 -1.22448
C 3.36748 1.51398 1.35395
C 3.20008 2.68867 0.62438
H 3.82019 1.54306 2.34026
H 3.51596 3.63864 1.04446
Cl 0.44547 -1.55848 2.10020

Single point energy calculations at SMD(Acetonitrile)/UM06-2x/6-311++G(d,p)

Single Point Energy ΔE (a.u.)

1a -594.9461543
A -588.4378958
B -1048.665225
TS-1 -1183.3829337
Int-1 -1183.423051
TS-2a -1183.397012
TS-2b -1183.396280

S84
 TS-3 -2232.083088
Int-2a -1183.436753
Int-2b -1183.437675
4a -1643.680639

9. References

(1) Woelk, K. J.; Dhake, K.; Schley, N. D.; Leitch, D. C. Chem Commun. 2023, 59, 13847-
13850.
(2) Bi, W.-Z.; Zhang, W.-J.; Li, Z.-J.; He, Y.-H.; Feng, S.-X.; Geng, Y.; Chen, X.-L.; Qu, L.-B.
Org. Biomol. Chem. 2021, 19, 8701-8705.
(3) Ogata, T.; Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 13848-13849.
(4) Khalifa, A.; Giles, M.; Ali, H. I.; Mohamady, S. Eur. J. Org. Chem. 2023, 26, e202300207.
(5) Wang, L.; Yu, Y.; Deng, L.; Du, K. Org. Lett. 2023, 25, 2349-2354.
(6) Cristau, H.-J.; Lambert, J.-M.; Pirat, J.-L. Synthesis 1998, 1998, 1167-1170.
(7) Li, C.; Qi, Z.-C.; Yang, Q.; Qiang, X.-Y.; Yang, S.-D. Chin. J. Chem. 2018, 36, 1052-1058.
(8) Rocaboy, R.; Dailler, D.; Zellweger, F.; Neuburger, M.; Salomé, C.; Clot, E.; Baudoin, O.
Angew. Chem. Int. Ed. 2018, 57, 12131-12135.
(9) Gaussian 16 Rev. C.01; Wallingford, CT, 2016.
(10) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378-6396.
(11) Ernouf, G.; Chirkin, E.; Rhyman, L.; Ramasami, P.; Cintrat, J.-C. Angew. Chem. Int. Ed.
2020, 59, 2618-2622.
(12) Fukui, K. Acc. Chem. Res. 1981, 14, 363-368.
(13) C. Y. Legault, CYLview, version 1.0b, Universite de Sherbrooke, 2009.

S85
10. Spectra for new compounds
1H NMR (400 MHz, CDCl3) spectra of compound 1b (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1b

S86
1H NMR (400 MHz, CDCl3) spectra of compound 1c (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1c

S87
1H NMR (400 MHz, CDCl3) spectra of compound 1d (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1d

S88
19F NMR (376 MHz, CDCl3) spectra of compound 1d

S89
1H NMR (400 MHz, CDCl3) spectra of compound 1e (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1e

S90
1H NMR (400 MHz, CDCl3) spectra of compound 1f (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1f

S91
1H NMR (400 MHz, CDCl3) spectra of compound 1g (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1g

S92
1H NMR (400 MHz, CDCl3) spectra of compound 1h (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 1h

S93
1H NMR (600 MHz, CDCl3) spectra of compound 2h (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 2h

S94
1H NMR (400 MHz, CDCl3) spectra of compound 2k (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 2k

S95
1H NMR (600 MHz, CDCl3) spectra of compound 2o (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 2o

S96
1H NMR (400 MHz, CDCl3) spectra of compound 2p (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 2p

S97
1H NMR (400 MHz, CDCl3) spectra of compound 2q (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 2q

S98
31P NMR (162 MHz, CDCl3) spectra of compound 2q

S99
1H NMR (400 MHz, CDCl3) spectra of compound 3a (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3a (major)

S100
19F NMR (376 MHz, CDCl3) spectra of compound 3a (major)

S101
1H NMR (400 MHz, CDCl3) spectra of compound 3a (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3a (minor)

S102
19F NMR (376 MHz, CDCl3) spectra of compound 3a (minor)

S103
1H NMR (400 MHz, CDCl3) spectra of compound 3b (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3b (major)

S104
1H NMR (400 MHz, CDCl3) spectra of compound 3b (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3b (minor)

S105
1H NMR (400 MHz, CDCl3) spectra of compound 3c (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3c (major)

S106
1H NMR (400 MHz, CDCl3) spectra of compound 3c (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3c (minor)

S107
1H NMR (400 MHz, CDCl3) spectra of compound 3d (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3d (major)

S108
1H NMR (400 MHz, CDCl3) spectra of compound 3d (minor)

13C NMR (151 MHz, CDCl3) spectra of compound 3d (minor)

S109
1H NMR (400 MHz, CDCl3) spectra of compound 3e (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3e (major)

S110
19F NMR (376 MHz, CDCl3) spectra of compound 3e (major)

S111
1H NMR (400 MHz, CDCl3) spectra of compound 3e (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3e (minor)

S112
19F NMR (376 MHz, CDCl3) spectra of compound 3e (minor)

S113
1H NMR (400 MHz, CDCl3) spectra of compound 3f (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3f (major)

S114
1H NMR (400 MHz, CDCl3) spectra of compound 3f (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3f (minor)

S115
1H NMR (400 MHz, CDCl3) spectra of compound 3g (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3g (major)

S116
1H NMR (400 MHz, CDCl3) spectra of compound 3g (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3g (minor)

S117
1H NMR (400 MHz, CDCl3) spectra of compound 3h (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3h (major)

S118
1H NMR (400 MHz, CDCl3) spectra of compound 3h (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3h (minor)

S119
1H NMR (400 MHz, CDCl3) spectra of compound 3i (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3i (major)

S120
1H NMR (400 MHz, CDCl3) spectra of compound 3i (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3i (minor)

S121
1H NMR (400 MHz, CDCl3) spectra of compound 3j (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3j (major)

S122
1H NMR (400 MHz, CDCl3) spectra of compound 3j (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3j (minor)

S123
1H NMR (400 MHz, CDCl3) spectra of compound 3k (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3k (major)

S124
1H NMR (400 MHz, CDCl3) spectra of compound 3k (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3j (minor)

S125
1H NMR (400 MHz, CDCl3) spectra of compound 3l (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3l (major)

S126
1H NMR (400 MHz, CDCl3) spectra of compound 3l (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3l (minor)

S127
1H NMR (600 MHz, CDCl3) spectra of compound 3m (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 3m

S128
1H NMR (400 MHz, CDCl3) spectra of compound 3n (major) (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 3n (major)

S129
1H NMR (400 MHz, CDCl3) spectra of compound 3n (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3n (minor)

S130
1H NMR (600 MHz, CDCl3) spectra of compound 3o (major) (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 3o (major)

S131
1H NMR (600 MHz, CDCl3) spectra of compound 3o (minor)

13C NMR (151 MHz, CDCl3) spectra of compound 3o (minor)

S132
1H NMR (400 MHz, CDCl3) spectra of compound 3p (major) (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 3p (major)

S133
1H NMR (400 MHz, CDCl3) spectra of compound 3p (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3p (minor)

S134
1H NMR (400 MHz, CDCl3) spectra of compound 3q (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3q (major)

S135
1H NMR (400 MHz, CDCl3) spectra of compound 3q (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3q (minor)

S136
1H NMR (400 MHz, CDCl3) spectra of compound 3r (major) (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 3r (major)

S137
1H NMR (400 MHz, CDCl3) spectra of compound 3r (minor)

13C NMR (151 MHz, CDCl3) spectra of compound 3r (minor)

S138
1H NMR (600 MHz, CDCl3) spectra of compound 3s (major) (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 3s (major)

S139
1H NMR (400 MHz, CDCl3) spectra of compound 3s (minor)

13C NMR (101 MHz, CDCl3) spectra of compound 3s (minor)

S140
1H NMR (400 MHz, CDCl3) spectra of compound 5a (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 5a

S141
31P NMR (162 MHz, CDCl3) spectra of compound 5a

S142
1H NMR (400 MHz, CDCl3) spectra of compound 5b (major) (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 5b (major)

S143
31P NMR (243 MHz, CDCl3) spectra of compound 5b (major)

S144
1H NMR (400 MHz, CDCl3) spectra of compound 5b (minor)

13C NMR (151 MHz, CDCl3) spectra of compound 5b (minor)

S145
31P NMR (243 MHz, CDCl3) spectra of compound 5b (minor)

S146
1H NMR (400 MHz, CDCl3) spectra of compound 5c (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 5c

S147
31P NMR (243 MHz, CDCl3) spectra of compound 5c

S148
1H NMR (400 MHz, CDCl3) spectra of compound 5d (major) (See Procedure)

** The impurity peaks at 3.8-3.7 ppm and at 0.7 ppm were unable to remove after two column
chromatography.
13C NMR (101 MHz, CDCl3) spectra of compound 5d (major)

S149
31P NMR (162 MHz, CDCl3) spectra of compound 5d (major)

S150
1H NMR (600 MHz, CDCl3) spectra of compound 5d (minor)

13C NMR (151 MHz, CDCl3) spectra of compound 5d (minor)

S151
31P NMR (243 MHz, CDCl3) spectra of compound 5d (minor)

S152
1H NMR (400 MHz, CDCl3) spectra of compound 6a (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 6a

S153
19F NMR (376 MHz, CDCl3) spectra of compound 6a

S154
1H NMR (400 MHz, CDCl3) spectra of compound 6b (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 6b

S155
19F NMR (376 MHz, CDCl3) spectra of compound 6b

S156
1H NMR (400 MHz, CDCl3) spectra of compound 6c (See Procedure)

13C NMR (101 MHz, CDCl3) spectra of compound 6c

S157
19F NMR (376 MHz, CDCl3) spectra of compound 6c

S158
1H NMR (400 MHz, CDCl3) spectra of compound 6d (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 6d

S159
19F NMR (376 MHz, CDCl3) spectra of compound 6c

S160
1H NMR (400 MHz, CDCl3) spectra of compound 7 (See Procedure)

13C NMR (151 MHz, CDCl3) spectra of compound 7

------ End of the Document ------

S161