Supplementary Materials for - Science Advances · Supplementary Materials for Electrochemical oxidative oxysulfenylation and aminosulfenylation of alkenes with hydrogen evolution

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Supplementary Materials for

Electrochemical oxidative oxysulfenylation and aminosulfenylation

of alkenes with hydrogen evolution

Yong Yuan, Yixuan Chen, Shan Tang, Zhiliang Huang, Aiwen Lei*

*Corresponding author. Email: [email protected]

Published 3 August 2018, Sci. Adv. 4, eaat5312 (2018)

DOI: 10.1126/sciadv.aat5312

This PDF file includes:

Table S1. Optimization of reaction conditions. Fig. S1. The experimental setup for electrolysis. Section S1. Procedure for gram-scale synthesis Section S2. The cross-coupling experiment Section S3. Detailed descriptions for products Section S4. Copies of product NMR spectra References (48, 49)

Table S1. Optimization of reaction conditions.

aStandard conditions: C anode, Pt cathode, constant current = 12 mA, 1a (0.5 mmol), 2a (1.0 mmol),

3a (0.7 mL, 35 equiv.), nBu4NBF4 (3.0 mmol), MeCN (10 mL), 40

oC, 4 h, isolated yields.

bn.d. =

not detected.

Fig. S1. The experimental setup for electrolysis.

Section S1. Procedure for gram-scale synthesis

In an oven-dried undivided three-necked bottle (150 mL) equipped with a stir bar, thiophenols (5.0

mmol), nBu4NBF4 (3.0 mmol) were combined and added. The bottle was equipped with graphite rod

(ϕ 6 mm, about 20 mm immersion depth in solution) as the anode and platinum plate (15 mm × 15

mm × 0.3 mm) as the cathode and was then charged with nitrogen. Under the protection of N2,

styrene (10 mmol), methanol (7 mL) and CH3CN (100 mL) were injected respectively into the tubes

via syringes. The reaction mixture was stirred and electrolyzed at a constant current of 12 mA at

40 °C for 40 h. When the reaction was finished, the pure product was obtained by flash column

chromatography on silica gel.

Section S2. The cross-coupling experiment

In an oven-dried undivided three-necked bottle (25 mL) equipped with a stir bar,

bis-(4-chlorophenyl) disulfide 8a (0.1 mmol), phenyl disulfide 8u (0.1 mmol), nBu4NBF4 (3.0 mmol)

were combined and added. The bottle was equipped with graphite rod (ϕ 6 mm, about 20 mm

immersion depth in solution) as the anode and platinum plate (15 mm × 15 mm × 0.3 mm) as the

cathode and was then charged with nitrogen. Under the protection of N2, CH3OH (0.7 mL) and

CH3CN (10 mL) were injected respectively into the tubes via syringes. The reaction mixture was

stirred and electrolyzed at a constant current of 12 mA at 40 °C for 2 h. After completion of the

reaction, the crude products were obtained by flash column chromatography on silica gel and then

were determined by GC-MS.

The GC-MS spectra of crude products

215.0 220.0 225.0 230.0 235.0 240.0 245.0 250.0 255.0 260.0 265.0 270.0 275.0 280.0 285.0 290.00

10

20

30

40

50

60%

252

218

281254

286

221 267264 290225 269235216 237 257232 279247241 273

Section S3. Detailed descriptions for products

(4-Chlorophenyl)(2-methoxy-2-phenylethyl)sulfane (4aa). The desired pure product was

obtained in 75% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.43 – 7.25 (m, 9H), 4.31

(dd, J = 8.2, 4.9 Hz, 1H), 3.32 (dd, J = 13.3, 8.2 Hz, 1H), 3.28 (s, 3H), 3.14 (dd, J = 13.3, 4.9 Hz, 1H).

13C NMR (100 MHz, CDCl3): δ 140.18, 135.08, 131.92, 130.62, 128.92, 128.56, 128.20, 126.66,

82.37, 56.99, 41.71. HRMS: m/z(EI) calculated [M]+: 278.0532, measured: 278.0533.

(4-Chlorophenyl)(2-methoxy-2-(p-tolyl)ethyl)sulfane (4ba). The desired pure product was


(dd, J = 8.1, 5.0 Hz, 1H), 3.28 (dd, J = 13.2, 8.2 Hz, 1H), 3.23 (s, 3H), 3.09 (dd, J = 13.2, 5.0 Hz, 1H),

2.35 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 138.00, 137.10, 135.11, 131.84, 130.53, 129.25,

128.90, 126.62, 82.12, 56.87, 41.63, 21.17. HRMS: m/z (EI) calculated [M]+: 290.0766, measured:

290.0773.

(2-(4-(Tert-butyl)phenyl)-2-methoxyethyl)(4-chlorophenyl)sulfane (4ca). The desired pure

product was obtained in 88% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.36 (d, J =

8.3 Hz, 2H), 7.25 – 7.19 (m, 6H), 4.26 (dd, J = 8.2, 4.8 Hz, 1H), 3.28 (dd, J = 13.3, 8.2 Hz, 1H), 3.24

(s, 3H), 3.11 (dd, J = 13.3, 4.9 Hz, 1H), 1.32 (s, 9H). 13

C NMR (100 MHz, CDCl3): δ 151.12, 137.07,

135.21, 131.80, 130.55, 128.86, 126.34, 125.41, 82.22, 56.97, 41.66, 34.53, 31.31. HRMS: m/z (EI)

calculated [M]+: 334.1158, measured: 334.1162.

(4-Chlorophenyl)(2-methoxy-2-(4-methoxyphenyl)ethyl)sulfane (4da). The desired pure

product was obtained in 77% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.30 – 7.23

(m, 6H), 6.92 (d, J = 8.7 Hz, 2H), 4.26 (dd, J = 8.0, 5.2 Hz, 1H), 3.84 (s, 3H), 3.32 (dd, J = 13.2, 8.0

Hz, 1H), 3.25 (s, 3H), 3.12 (dd, J = 13.2, 5.2 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 159.48,

135.13, 132.08, 131.82, 130.55, 128.88, 127.90, 113.88, 81.88, 56.71, 55.20, 41.60. HRMS: m/z (EI)


(4-Chlorophenyl)(2-(4-fluorophenyl)-2-methoxyethyl)sulfane (4ea). The desired pure product

was obtained in 78% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.30 – 7.23 (m,

6H), 7.08 – 7.01 (m, 2H), 4.26 (dd, J = 7.8, 5.3 Hz, 1H), 3.28 (dd, J = 13.3, 7.8 Hz, 1H), 3.22 (s,

3H), 3.07 (dd, J = 13.3, 5.3 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 162.52 (d, J = 246.4 Hz),

135.89 (d, J = 3.1 Hz), 134.84, 132.07, 130.72, 128.95, 128.34 (d, J = 8.2 Hz), 115.45 (d, J = 21.5

Hz), 81.73, 56.91, 41.67. 19

F NMR (377 MHz, CDCl3): δ -113.79. HRMS: m/z (EI) calculated

[M]+: 296.0438, measured: 296.0434.

(4-Chlorophenyl)(2-(4-chlorophenyl)-2-methoxyethyl)sulfane (4fa). The desired pure product

was obtained in 77% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.26 – 7.22 (m, 2H),

7.18 – 7.12 (m, 6H), 4.16 (dd, J = 7.7, 5.3 Hz, 1H), 3.21 – 3.15 (m, 1H), 3.14 (s, 3H), 2.97 (dd, J =

13.4, 5.3 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 138.64, 134.69, 133.88, 132.09, 130.75, 128.95,

128.71, 128.05, 81.70, 56.99, 41.52. HRMS: m/z (EI) calculated [M]+: 312.0142, measured:

312.0156.

(2-(4-Bromophenyl)-2-methoxyethyl)(4-chlorophenyl)sulfane (4ga). The desired pure product

was obtained in 62% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.48 (d, J = 8.4 Hz,

2H), 7.27 – 7.23 (m, 4H), 7.17 (d, J = 8.4 Hz, 2H), 4.23 (dd, J = 7.7, 5.4 Hz, 1H), 3.26 (dd, J = 13.1,

7.5 Hz, 1H), 3.23 (s, 3H), 3.06 (dd, J = 13.4, 5.3 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 139.22,

134.70, 132.21, 131.72, 130.85, 129.02, 128.44, 122.11, 81.84, 57.09, 41.57. HRMS: m/z (EI)


(4-Chlorophenyl)(2-methoxy-2-(naphthalen-2-yl)ethyl)sulfane (4ha). The desired pure product

was obtained in 81% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.88 (dd, J = 9.0,

6.1 Hz, 3H), 7.78 (s, 1H), 7.53 (dd, J = 8.7, 7.1 Hz, 2H), 7.48 (dd, J = 8.5, 1.6 Hz, 1H), 7.33 –

7.28 (m, 2H), 7.27 – 7.23 (m, 2H), 4.49 (dd, J = 8.0, 5.1 Hz, 1H), 3.46 – 3.39 (m, 1H), 3.33 (s,

3H), 3.23 (dd, J = 13.3, 5.1 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 137.53, 134.98, 133.30,

133.09, 131.99, 130.73, 128.92, 128.58, 127.84, 127.72, 126.29, 126.23, 126.12, 123.97, 82.57,

57.07, 41.57. HRMS: m/z (EI) calculated [M]+: 328.0689, measured: 328.0677.

(4-Chlorophenyl)(2-(2-chlorophenyl)-2-methoxyethyl)sulfane (4ia). The desired pure product


1H), 7.35 – 7.28 (m, 4H), 7.26 – 7.21 (m, 3H), 4.79 (dd, J = 8.6, 3.6 Hz, 1H), 3.28 (s, 3H), 3.23

(dd, J = 13.6, 3.7 Hz, 1H), 3.11 (dd, J = 13.6, 8.6 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 137.71,

134.83, 132.97, 132.12, 131.12, 129.56, 129.07, 128.85, 127.37, 127.24, 78.58, 57.44, 40.50.

HRMS: m/z (EI) calculated [M]+: 312.0142, measured: 312.0149.

(4-Chlorophenyl)(2-methoxy-2-(m-tolyl)ethyl)sulfane (4ja). The desired pure product was

obtained in 80% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.27 – 7.20 (m, 5H),

7.14 – 7.08 (m, 3H), 4.24 (dd, J = 8.3, 4.8 Hz, 1H), 3.28 (dd, J = 13.3, 8.3 Hz, 1H), 3.24 (s, 3H),

3.13 – 3.07 (m, 1H), 2.35 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 140.11, 138.26, 135.11, 131.87,

130.59, 128.97, 128.90, 128.44, 127.25, 123.78, 82.38, 57.00, 41.65, 21.42. HRMS: m/z (EI)


(4-Chlorophenyl)(2-methoxy-2-phenylpropyl)sulfane (4ka). The desired pure product was

obtained in 95% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.47 – 7.28 (m, 5H),

7.23 – 7.17 (m, 4H), 3.38 (d, J = 12.6 Hz, 1H), 3.26 (d, J = 12.6 Hz, 1H), 3.16 (s, 3H), 1.74 (s,

3H). 13

C NMR (100 MHz, CDCl3): δ 143.11, 135.96, 131.60, 130.50, 128.73, 128.31, 127.51,

126.27, 78.96, 50.84, 47.96, 22.13. HRMS: m/z (EI) calculated [M]+: 292.0689, measured:

292.0681.

(4-Chlorophenyl)(1-methoxy-2,3-dihydro-1H-inden-2-yl)sulfane (4la). The desired pure

product was obtained in 71% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.41 –

7.35 (m, 3H), 7.32 – 7.20 (m, 5H), 4.67 (d, J = 3.0 Hz, 1H), 3.95 (ddd, J = 7.3, 3.9, 3.2 Hz, 1H),

3.56 (dd, J = 16.8, 7.5 Hz, 1H), 3.40 (s, 3H), 2.86 (dd, J = 16.8, 4.0 Hz, 1H). 13

C NMR (100 MHz,

CDCl3): δ 141.51, 140.38, 133.88, 132.74, 132.00, 129.10, 129.04, 126.93, 125.61, 124.97, 89.26,

56.95, 50.46, 37.77. HRMS: m/z (EI) calculated [M]+: 290.0532, measured: 290.0535.

(4-Chlorophenyl)(1-methoxy-1-phenylpropan-2-yl)sulfane (4ma). The desired pure product


9H), 4.27 (d, J = 4.5 Hz, 1H), 3.41 – 3.33 (m, 1H), 3.28 (s, 3H), 1.24 (d, J = 6.9 Hz, 3H). 13

C

NMR (100 MHz, CDCl3): δ 139.26, 134.00, 133.31, 132.89, 128.93, 128.24, 127.80, 127.09,

85.57, 57.55, 50.30, 15.49. HRMS: m/z (EI) calculated [M]+: 292.0689, measured: 292.0695.

(4-Chlorophenyl)(2-methoxycyclohexyl)sulfane (4na). The desired pure product was obtained

in 22% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.38 (d, J = 8.5 Hz, 2H), 7.28 –

7.22 (m, 2H), 3.38 (s, 3H), 3.14 – 3.03 (m, 2H), 2.19 – 2.10 (m, 1H), 2.04 – 1.94 (m, 1H), 1.76 –

1.62 (m, 2H), 1.37 – 1.22 (m, 4H). 13

C NMR (100 MHz, CDCl3): δ 133.66, 133.62, 132.82,

128.81, 81.74, 56.58, 51.66, 31.51, 29.93, 24.84, 23.35. HRMS: m/z (EI) calculated [M]+:

256.0689, measured: 256.0694.

(4-Chlorophenyl)(2-ethyl-2-methoxybutyl)sulfane (4oa). The desired pure product was obtained

in 20% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.31 – 7.27 (m, 2H), 7.25 – 7.21

(m, 2H), 3.15 (s, 3H), 3.01 (s, 2H), 1.64 – 1.57 (m, 4H), 0.83 (t, J = 7.5 Hz, 6H). 13

C NMR (100

MHz, CDCl3): δ 136.09, 131.73, 130.60, 128.88, 78.86, 48.79, 39.08, 26.18, 7.45. HRMS: m/z (EI)


1-(2-((4-Chlorophenyl)thio)-1-methoxyethyl)pyrrolidin-2-one (4pa). The desired pure product


2H), 7.29 – 7.24 (m, 2H), 5.28 (dd, J = 7.8, 5.7 Hz, 1H), 3.38 – 3.29 (m, 1H), 3.24 (s, 3H), 3.22 –

3.12 (m, 2H), 3.00 (dd, J = 13.8, 7.7 Hz, 1H), 2.52 – 2.36 (m, 2H), 2.07 – 1.87 (m, 2H). 13

C NMR

(100 MHz, CDCl3): δ 176.23, 133.40, 132.97, 132.15, 129.01, 81.43, 55.79, 40.84, 36.49, 31.34,

18.02. HRMS: m/z (EI) calculated [M]+: 285.0590, measured: 285.0588.

(2-Methoxy-2-phenylethyl)(p-tolyl)sulfane (4ab).23

The desired pure product was obtained in 50%

yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.24 (m, 7H), 7.09 (d, J = 7.9 Hz,

2H), 4.26 (dd, J = 8.2, 5.0 Hz, 1H), 3.29 (dd, J = 7.3, 6.0 Hz, 1H), 3.25 (s, 3H), 3.09 (dd, J = 13.3,

4.9 Hz, 1H), 2.32 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 140.49, 136.15, 132.58, 130.10, 129.63,

128.47, 128.04, 126.68, 82.34, 56.98, 42.16, 20.97.

(2-Methoxy-2-phenylethyl)(naphthalen-2-yl)sulfane (4bb). The desired pure product was


7.72 (t, J = 7.9 Hz, 3H), 7.47 – 7.32 (m, 8H), 4.35 (dd, J = 8.1, 5.0 Hz, 1H), 3.45 – 3.38 (m, 1H),

3.27 – 3.21 (m, 4H). 13

C NMR (100 MHz, CDCl3): δ 140.45, 134.00, 133.71, 131.68, 128.57,

128.35, 128.19, 127.66, 127.38, 127.02, 126.83, 126.73, 126.50, 125.61, 82.34, 57.06, 41.30.

HRMS: m/z (EI) calculated [M]+: 294,1078 measured: 294.1073.

(4-Fluorophenyl)(2-methoxy-2-phenylethyl)sulfane (4cb). The desired pure product was


– 6.94 (m, 2H), 4.25 (dd, J = 8.2, 5.0 Hz, 1H), 3.26 (dd, J = 11.6, 6.5 Hz, 1H), 3.24 (s, 3H), 3.07 (dd,

J = 13.3, 4.9 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ161.74 (d, J = 246.3 Hz), 140.29, 132.44 (d, J

= 8.0 Hz), 131.30 (d, J = 3.4 Hz), 128.55, 128.17, 126.71, 115.95 (d, J = 21.8 Hz), 82.48, 56.99,

42.83. 19

F NMR (377 MHz, CDCl3): δ -115.54. HRMS: m/z (EI) calculated [M]+: 262.0828,

measured: 262.0834.

(4-Bromophenyl)(2-methoxy-2-phenylethyl)sulfane (4db). The desired pure product was



3.10 (dd, J = 13.3, 4.9 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 140.16, 135.79, 131.81, 130.73,

128.56, 128.21, 126.64, 119.74, 82.34, 56.99, 41.50. HRMS: m/z (EI) calculated [M]+: 322.0027,

measured: 322.0038.

(2-Methoxy-2-phenylethyl)(4-(trifluoromethyl)phenyl)sulfane (4eb). The desired pure product


2H), 7.45 – 7.35 (m, 7H), 4.39 (dd, J = 8.1, 4.9 Hz, 1H), 3.41 (dd, J = 13.3, 8.2 Hz, 1H), 3.31 (s, 3H),

3.24 (dd, J = 13.3, 4.9 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 142.21, 140.02, 128.64, 128.34,

127.52, 127.45 (q, J = 32.5 Hz), 126.63, 125.54 (q, J = 3.8 Hz), 124.11 (q, J = 270 Hz), 82.30, 57.02,

40.27. 19


measured: 312.0811.

(3-Bromophenyl)(2-methoxy-2-phenylethyl)sulfane (4fb). The desired pure product was

obtained in 72% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.42 (t, J = 1.8 Hz, 1H),

7.39 – 7.21 (m, 7H), 7.13 – 7.08 (m, 1H), 4.31 (dd, J = 8.1, 4.9 Hz, 1H), 3.31 (dd, J = 13.3, 8.1 Hz,

1H), 3.25 (s, 3H), 3.13 (dd, J = 13.2, 4.9 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 140.11, 139.14,

131.19, 130.07, 128.81, 128.59, 128.27, 127.33, 126.66, 122.70, 82.34, 57.02, 41.17. HRMS: m/z

(EI) calculated [M]+: 322.0027, measured: 322.0020.

(3-Chlorophenyl)(2-methoxy-2-phenylethyl)sulfane (4gb). The desired pure product was



3.13 (dd, J = 13.2, 4.9 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 140.14, 138.89, 134.54, 129.76,

128.57, 128.40, 128.24, 126.86, 126.66, 125.90, 82.40, 56.99, 41.15. HRMS: m/z (EI) calculated

[M]+: 278.0532, measured: 278.0534.

(2-Methoxy-2-phenylethyl)(o-tolyl)sulfane (4hb). The desired pure product was obtained in 66%

yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.44 – 7.31 (m, 6H), 7.23 – 7.10 (m,


4.8 Hz, 1H), 2.42 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 140.54, 137.70, 135.75, 130.07, 128.54,


[M]+: 258.1078, measured: 258.1089.

(2-Chlorophenyl)(2-methoxy-2-phenylethyl)sulfane (4ib). The desired pure product was



3.13 (dd, J = 13.0, 4.6 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 140.32, 135.88, 133.83, 129.65,


278.0532, measured: 278.0529.

(3,4-Dichlorophenyl)(2-methoxy-2-phenylethyl)sulfane (4jb). The desired pure product was


7.12 (dd, J = 8.4, 2.2 Hz, 1H), 4.30 (dd, J = 8.1, 4.9 Hz, 1H), 3.32 – 3.26 (m, 1H), 3.25 (s, 3H),

3.12 (dd, J = 13.3, 4.9 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 139.94, 137.09, 132.70, 130.39,


[M]+: 312.0142, measured: 312.0146.

(2-Methoxy-2-phenylethyl)(phenyl)sulfane (4kb).23


yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.24 (m, 9H), 7.17 (t, J = 7.3 Hz,


4.9 Hz, 1H). 113

C NMR (100 MHz, CDCl3): δ 140.42, 136.47, 129.25, 128.85, 128.53, 128.13,

126.69, 125.97, 82.37, 57.02, 41.47.

Benzyl(2-methoxy-2-phenylethyl)sulfane (4lb). The desired pure product was obtained in 40%

yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.37 – 7.19 (m, 10H), 4.18 (dd, J = 7.9,

5.1 Hz, 1H), 3.71 – 3.59 (m, 2H), 3.22 (s, 3H), 2.82 (dd, J = 13.7, 8.0 Hz, 1H), 2.59 (dd, J = 13.7,

5.1 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 140.82, 138.45, 128.97, 128.43, 128.39, 127.96,


258.1072.

Cyclohexyl(2-methoxy-2-phenylethyl)sulfane (4mb). The desired pure product was obtained in

37% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.28 (m, 5H), 4.26 (dd, J =

8.0, 5.2 Hz, 1H), 3.25 (s, 3H), 2.95 (dd, J = 13.2, 8.0 Hz, 1H), 2.73 (dd, J = 13.2, 5.2 Hz, 1H),

2.59 – 2.49 (m, 1H), 1.98 – 1.87 (m, 2H), 1.79 – 1.67 (m, 2H), 1.65 – 1.52 (m, 1H), 1.34 – 1.17 (m,

5H). 13

C NMR (100 MHz, CDCl3): δ 141.00, 128.41, 127.94, 126.71, 84.09, 56.90, 44.18, 37.71,

33.62, 26.07, 25.78. HRMS: m/z (EI) calculated [M]+: 250.1391, measured: 250.1387.

(2-Butoxy-2-phenylethyl)(4-chlorophenyl)sulfane (4ac). The desired pure product was obtained

in 76% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.38 – 7.29 (m, 5H), 7.27 – 7.20

(m, 4H), 4.37 (dd, J = 8.2, 4.9 Hz, 1H), 3.38 – 3.22 (m, 3H), 3.08 (dd, J = 13.2, 4.9 Hz, 1H), 1.57

– 1.48 (m, 2H), 1.41 – 1.29 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H). 13

C NMR (100 MHz, CDCl3): δ

141.00, 135.42, 131.72, 130.42, 128.85, 128.49, 128.03, 126.58, 80.84, 69.08, 41.86, 31.78, 19.29,


(2-(2-Chloroethoxy)-2-phenylethyl)(4-chlorophenyl)sulfane (4bc). The desired pure product


9H), 4.44 (dd, J = 8.1, 5.0 Hz, 1H), 3.63 – 3.52 (m, 4H), 3.33 (dd, J = 13.5, 8.1 Hz, 1H), 3.11 (dd,

J = 13.5, 5.0 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 140.01, 135.04, 132.00, 130.69, 128.94,

128.65, 128.40, 126.65, 81.55, 69.21, 42.73, 41.73. HRMS (ESI) calculated for C16H20Cl2NOS

[M+NH4]+: 344.0637; found: 344.0638.

2-(2-((4-Chlorophenyl)thio)-1-phenylethoxy)ethanol (4cc). The desired pure product was


4.41 (dd, J = 8.9, 4.2 Hz, 1H), 3.72 – 3.65 (m, 2H), 3.55 – 3.50 (m, 1H), 3.41 – 3.35 (m, 1H), 3.28

(dd, J = 13.6, 8.9 Hz, 1H), 3.12 (dd, J = 13.6, 4.2 Hz, 1H), 2.32 (s, 1H). . 13

C NMR (100 MHz,

CDCl3): δ 140.27, 134.76, 132.24, 130.81, 129.06, 128.68, 128.31, 126.42, 81.18, 70.42, 61.70,

42.14. HRMS (ESI) calculated for C16H21ClNO2S [M+NH4]+: 326.0976; found: 326.0975.

(4-Chlorophenyl)(2-(3-(2-methoxyethoxy)propoxy)-2-phenylethyl)sulfane (4dc). The desired

pure product was obtained in 63% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.36

– 7.20 (m, 9H), 4.44 (dd, J = 7.9, 5.3 Hz, 1H), 3.65 – 3.58 (m, 4H), 3.55 – 3.47 (m, 4H), 3.37 (s,

3H), 3.32 (dd, J = 13.4, 7.9 Hz, 1H), 3.10 (dd, J = 13.4, 5.3 Hz, 1H). 13

C NMR (100 MHz, CDCl3):

δ 140.42, 135.21, 131.79, 130.57, 128.83, 128.46, 128.10, 126.69, 81.26, 71.87, 70.40, 70.39,

68.46, 58.97, 41.62. HRMS (ESI) calculated for C19H27ClNO3S [M+NH4]+: 384.1395; found:

384.1393.

(4-Chlorophenyl)(2-isopropoxy-2-phenylethyl)sulfane (4ec). The desired pure product was


4.50 (dd, J = 8.4, 4.8 Hz, 1H), 3.55 – 3.45 (m, 1H), 3.25 (dd, J = 13.2, 8.4 Hz, 1H), 3.10 – 3.04 (m,

1H), 1.14 (d, J = 6.0 Hz, 3H), 1.08 (d, J = 6.2 Hz, 3H). 13

C NMR (100 MHz, CDCl3): δ 141.75,

135.54, 131.62, 130.25, 128.85, 128.43, 127.92, 126.54, 77.95, 69.75, 42.09, 23.25, 21.19. HRMS:

m/z (EI) calculated [M]+: 306.0845, measured: 306.0846.

(4-Chlorophenyl)(2-(cyclohexyloxy)-2-phenylethyl)sulfane (4fc). The desired pure product was


4.56 (dd, J = 8.4, 4.5 Hz, 1H), 3.30 – 3.15 (m, 2H), 3.10 – 3.02 (m, 1H), 1.84 – 1.13 (m, 10H). 13

C

NMR (100 MHz, CDCl3): δ 141.95, 135.73, 131.54, 130.14, 128.83, 128.41, 127.85, 126.51,

77.64, 75.57, 42.26, 33.31, 31.22, 25.70, 24.03, 23.84. HRMS (ESI) calculated for C20H27ClNOS

[M+NH4]+: 364.1496; found: 364.1496.

(2-(Tert-butoxy)-2-phenylethyl)(4-chlorophenyl)sulfane (4gc). The desired pure product was


7.26 – 7.20 (m, 5H), 4.61 (dd, J = 8.5, 4.6 Hz, 1H), 3.18 (dd, J = 13.3, 8.5 Hz, 1H), 3.03 (dd, J =

13.3, 4.6 Hz, 1H), 1.11 (s, 9H). 13

C NMR (100 MHz, CDCl3): δ 144.54, 135.90, 131.36, 129.88,


320.1002, measured: 320.1010.

2-((4-Chlorophenyl)thio)-1-phenylethyl acetate(4hc).48

The desired pure product was obtained

in 39% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.43 – 7.25 (m, 9H), 4.31 (dd, J

= 8.2, 4.9 Hz, 1H), 3.32 (dd, J = 13.3, 8.2 Hz, 1H), 3.28 (s, 3H), 3.14 (dd, J = 13.3, 4.9 Hz, 1H).

13C NMR (100 MHz, CDCl3): δ 169.95, 138.66, 134.02, 132.60, 131.42, 129.07, 128.56, 128.49,

126.59, 74.35, 40.21, 20.99.

2-((4-Chlorophenyl)thio)-1-phenylethanol (4ic).49


yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.42 – 7.28 (m, 9H), 4.78 – 4.72 (m,

1H), 3.31 (dd, J = 13.8, 3.7 Hz, 1H), 3.14 (dd, J = 13.8, 9.2 Hz, 1H), 2.84 (d, J = 2.5 Hz, 1H). 13

C

NMR (100 MHz, CDCl3): δ 141.90, 133.50, 132.73, 131.41, 129.19, 128.57, 128.07, 125.78,

71.72, 43.99.

N-(2-((4-Chlorophenyl)thio)-1-phenylethyl)-4-methylaniline (6aa). The desired pure product


9H), 6.95 (d, J = 8.3 Hz, 2H), 6.47 (d, J = 8.2 Hz, 2H), 4.45 (s, 1H), 4.41 (dd, J = 9.1, 4.4 Hz, 1H),

3.39 (dd, J = 13.5, 4.4 Hz, 1H), 3.19 (dd, J = 13.4, 9.1 Hz, 1H), 2.25 (s, 3H). 13

C NMR (100 MHz,

CDCl3): δ 144.64, 142.23, 133.47, 132.87, 131.86, 129.55, 129.17, 128.81, 127.57, 127.13, 126.31,

113.86, 57.18, 42.76, 20.34. HRMS: m/z (EI) calculated [M]+: 353.1005, measured: 353.1010.

N-(2-((4-Chlorophenyl)thio)-1-(4-methoxyphenyl)ethyl)-4-methylaniline (6ba). The desired

pure product was obtained in 61% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.38

– 7.26 (m, 6H), 6.97 (d, J = 8.3 Hz, 2H), 6.92 (d, J = 8.6 Hz, 2H), 6.49 (d, J = 8.3 Hz, 2H), 4.46 –

4.35 (m, 2H), 3.84 (s, 3H), 3.37 (dd, J = 13.4, 4.7 Hz, 1H), 3.19 (dd, J = 13.4, 8.8 Hz, 1H), 2.26 (s,

3H). 13

C NMR (100 MHz, CDCl3): δ 158.90, 144.67, 134.09, 133.61, 132.70, 131.71, 129.52,

129.10, 127.37, 127.02, 114.12, 113.85, 56.56, 55.16, 42.67, 20.32. HRMS (ESI) calculated for

C22H23ClNOS [M+H]+: 384.1183; found: 384.1184.

N-(1-((4-chlorophenyl)thio)-2-phenylpropan-2-yl)-4-methylaniline (6ca). The desired pure


7.57 (m, 2H), 7.47 – 7.23 (m, 7H), 6.89 (d, J = 8.1 Hz, 2H), 6.36 – 6.29 (m, 2H), 4.48 (s, 1H),

3.57 – 3.44 (m, 2H), 2.25 (s, 3H), 1.79 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 145.54, 142.96,

135.05, 132.30, 131.21, 129.22, 128.99, 128.68, 127.03, 126.98, 125.95, 116.00, 58.90, 48.90,


N-(2-((4-chlorophenyl)thio)-1-(4-fluorophenyl)ethyl)-4-methylaniline (6da). The desired pure

product was obtained in 48% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.42 – 7.28

(m, 6H), 7.10 – 7.04 (m, 2H), 6.98 (d, J = 8.1 Hz, 2H), 6.49 – 6.44 (m, 2H), 4.46 (s, 1H), 4.40 (dd, J

= 9.0, 4.5 Hz, 1H), 3.36 (dd, J = 13.5, 4.5 Hz, 1H), 3.17 (dd, J = 13.5, 9.0 Hz, 1H), 2.27 (s, 3H). 13

C

NMR (100 MHz, CDCl3): δ 163.27, 160.83, 144.42, 137.88 (d, J = 3.1 Hz), 133.11 (d, J = 22.7 Hz),

131.95, 129.57, 129.20, 127.86 (d, J = 8.1 Hz), 127.32, 115.65 (d, J = 21.5 Hz), 113.88, 56.51, 42.83,

20.32. 19


measured: 371.0916.

4-Methyl-N-(1-phenyl-2-((4-(trifluoromethyl)phenyl)thio)ethyl)aniline (6ea). The desired pure

product was obtained in 58% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.56 (d, J =

8.3 Hz, 2H), 7.46 – 7.28 (m, 7H), 6.96 (d, J = 8.1 Hz, 2H), 6.49 (d, J = 8.4 Hz, 2H), 4.55 (dd, J = 8.6,

4.7 Hz, 1H), 4.40 (s, 1H), 3.49 (dd, J = 13.3, 4.7 Hz, 1H), 3.32 (dd, J = 13.3, 8.7 Hz, 1H), 2.25 (s,

3H). 13

C NMR (100 MHz, CDCl3): δ 144.46, 141.98, 140.81, 129.61, 128.88, 128.57, 128.10 (q, J =

32.6 Hz), 127.73, 127.31, 126.32, 125.75 (q, J = 3.8 Hz), 124.00 (q, J = 270 Hz), 113.90, 57.16,

41.14, 20.33. 19


measured: 387.1259.

4-Chloro-N-(2-((4-chlorophenyl)thio)-1-phenylethyl)aniline (6fa). The desired pure product


9H), 7.10 – 7.03 (m, 2H), 6.47 – 6.41 (m, 2H), 4.58 (s, 1H), 4.36 (dd, J = 9.1, 4.1 Hz, 1H), 3.39

(dd, J = 13.6, 4.3 Hz, 1H), 3.15 (dd, J = 13.6, 9.3 Hz, 1H). 13

C NMR (100 MHz, CDCl3): δ 145.50,

141.57, 133.17, 133.05, 132.11, 129.28, 128.94, 128.90, 127.80, 126.20, 122.61, 114.83, 57.02,


N-(2-((4-chlorophenyl)thio)-1-phenylethyl)-N,4-dimethylaniline (6ga). The desired pure


7.25 (m, 9H), 7.09 (d, J = 8.5 Hz, 2H), 6.74 (d, J = 8.5 Hz, 2H), 5.10 (t, J = 7.6 Hz, 1H), 3.59 (dd,

J = 13.1, 6.7 Hz, 1H), 3.52 (dd, J = 13.1, 8.4 Hz, 1H), 2.71 (s, 3H), 2.33 (s, 3H). 13

C NMR (100

MHz, CDCl3): δ 147.95, 139.29, 134.59, 132.29, 131.33, 129.64, 128.96, 128.45, 127.44, 127.31,


367.1153.

1-(2-((4-Chlorophenyl)thio)-1-phenylethyl)-1H-pyrazole (6ha). The desired pure product was

obtained in 48% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.62 (d, J = 1.6 Hz,

1H), 7.41 (d, J = 2.1 Hz, 1H), 7.40 – 7.28 (m, 9H), 6.29 (t, J = 2.1 Hz, 1H), 5.38 (dd, J = 9.0, 5.9

Hz, 1H), 4.04 (dd, J = 13.8, 9.0 Hz, 1H), 3.64 (dd, J = 13.8, 5.9 Hz, 1H). 13

C NMR (100 MHz,

CDCl3): δ 139.66, 138.95, 133.62, 132.72, 131.63, 129.33, 129.12, 128.75, 128.37, 126.87, 105.57,


N-(2-((4-chlorophenyl)thio)-1-phenylethyl)acetamide (6ia).48

The desired pure product was


6.12 (d, J = 6.9 Hz, 1H), 5.20 – 5.13 (m, 1H), 3.44 (dd, J = 13.5, 6.7 Hz, 1H), 3.28 (dd, J = 13.6,

6.8 Hz, 1H), 2.00 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 169.64, 139.93, 134.00, 132.40, 130.98,

129.10, 128.80, 128.00, 126.66, 52.87, 39.64, 23.24.

N-(2-((4-chlorophenyl)thio)-1-phenylethyl)butan-1-amine (6ja). The desired pure product was


3.73 (dd, J = 9.2, 4.4 Hz, 1H), 3.24 (dd, J = 13.3, 4.4 Hz, 1H), 3.07 (dd, J = 13.3, 9.2 Hz, 1H),

2.51 – 2.39 (m, 2H), 1.92 (s, 1H), 1.50 – 1.41 (m, 2H), 1.39 – 1.28 (m, 2H), 0.90 (t, J = 7.3 Hz,

3H). 13

C NMR (100 MHz, CDCl3): δ 142.63, 134.29, 132.26, 131.03, 129.04, 128.52, 127.52,

127.06, 61.58, 47.37, 42.46, 32.13, 20.34, 13.94. HRMS (ESI) calculated for C18H23ClNS [M+H]+:

320.1234; found: 320.1234.

N-benzyl-2-((4-chlorophenyl)thio)-1-phenylethanamine (6ka). The desired pure product was


3.81 – 3.71 (m, 2H), 3.52 (d, J = 13.4 Hz, 1H), 3.23 (dd, J = 13.5, 4.0 Hz, 1H), 3.06 (dd, J = 13.4,

9.6 Hz, 1H), 2.30 (s, 1H). 13

C NMR (100 MHz, CDCl3): δ 142.24, 140.11, 133.90, 132.43, 131.44,

129.03, 128.66, 128.36, 128.10, 127.69, 127.25, 126.90, 60.01, 51.24, 42.74. HRMS (ESI)

calculated for C21H21ClNS [M+H]+: 354.1078; found: 354.1080.

N-(2-((4-chlorophenyl)thio)-1-phenylethyl)cyclopropanamine(6la). The desired pure product


9H), 3.87 (dd, J = 7.8, 5.9 Hz, 1H), 3.26 – 3.13 (m, 2H), 2.15 (s, 1H), 2.05 – 1.94 (m, 1H), 0.44 –

0.26 (m, 4H). 13

C NMR (100 MHz, CDCl3): δ 142.75, 134.59, 132.07, 130.76, 128.99, 128.44,

127.52, 127.17, 62.08, 41.53, 29.26, 6.79, 6.12. HRMS: m/z (EI) calculated [M]+: 303.0838,

measured: 303.0833.

1-(((4-Chlorophenyl)thio)oxy)-2,2,6,6-tetramethylpiperidine (7a). The desired pure product

was obtained in 30% yield as a white solid. 1H NMR (400 MHz, CDCl3): δ 7.64 – 7.57 (m, 2H),

7.44 – 7.39 (m, 2H), 1.90 – 1.39 (m, 15H), 0.94 (s, 3H). 13

C NMR (100 MHz, CDCl3): δ 148.85,

135.59, 128.65, 127.40, 61.41, 58.92, 43.39, 41.28, 35.32, 32.66, 28.67, 27.84, 17.16. HRMS (ESI)

calculated for C15H23ClNOS [M+H]+: 300.1183; found: 300.1183.

(4-Chlorophenyl)(2-cyclopropyl-2-methoxy-2-phenylethyl)sulfane (4qa). The desired pure

product was obtained in 63% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.42 (d, J

= 7.5 Hz, 2H), 7.35 (t, J = 7.4 Hz, 2H), 7.30 – 7.19 (m, 5H), 3.60 – 3.37 (m, 2H), 3.24 (s, 3H),

1.48 – 1.37 (m, 1H), 0.61 – 0.37 (m, 3H), 0.34 – 0.25 (m, 1H). 13


141.04, 136.16, 131.63, 130.46, 128.81, 127.89, 127.37, 127.02, 80.09, 50.88, 42.39, 19.58, 2.60,


(4-Chlorophenyl)(5-methoxy-2-phenylpent-2-en-1-yl)sulfane (9a). The desired pure product


2H), 7.33 (t, J = 7.4 Hz, 2H), 7.30 – 7.22 (m, 5H), 5.88 (t, J = 7.3 Hz, 1H), 3.97 (s, 2H), 3.37 (dd,

J = 13.0, 6.2 Hz, 2H), 3.33 (s, 3H), 2.37 (q, J = 6.9 Hz, 2H). 13


141.23, 135.92, 134.75, 132.69, 132.21, 129.11, 128.88, 128.34, 127.28, 126.21, 71.85, 58.69,


Section S4. Copies of product NMR spectra

1H NMR of compound 4aa

13C NMR of compound 4aa

1H NMR of compound 4ba

13C NMR of compound 4ba

1H NMR of compound 4ca

13C NMR of compound 4ca

1H NMR of compound 4da

13C NMR of compound 4da

1H NMR of compound 4ea

13C NMR of compound 4ea

19F NMR of compound 4ea

1H NMR of compound 4fa

13C NMR of compound 4fa

1H NMR of compound 4ga

13C NMR of compound 4ga

1H NMR of compound 4ha

13C NMR of compound 4ha

1H NMR of compound 4ia

13C NMR of compound 4ia

1H NMR of compound 4ja

13C NMR of compound 4ja

1H NMR of compound 4ka

13C NMR of compound 4ka

1H NMR of compound 4la

13C NMR of compound 4la

1H NMR of compound 4ma

13C NMR of compound 4ma

1H NMR of compound 4na

13C NMR of compound 4na

1H NMR of compound 4oa

13C NMR of compound 4oa

1H NMR of compound 4pa

13C NMR of compound 4pa

1H NMR of compound 4ab

13C NMR of compound 4ab

1H NMR of compound 4bb

13C NMR of compound 4bb

1H NMR of compound 4cb

13C NMR of compound 4cb

19F NMR of compound 4cb

1H NMR of compound 4db

13C NMR of compound 4db

1H NMR of compound 4eb

13C NMR of compound 4eb

19F NMR of compound 4eb

1H NMR of compound 4fb

13C NMR of compound 4fb

1H NMR of compound 4gb

13C NMR of compound 4gb

1H NMR of compound 4hb

13C NMR of compound 4hb

1H NMR of compound 4ib

13C NMR of compound 4ib

1H NMR of compound 4jb

13C NMR of compound 4jb

1H NMR of compound 4kb

13C NMR of compound 4kb

1H NMR of compound 4lb

13C NMR of compound 4lb

1H NMR of compound 4mb

13C NMR of compound 4mb

1H NMR of compound 4ac

13C NMR of compound 4ac

1H NMR of compound 4bc

13C NMR of compound 4bc

1H NMR of compound 4cc

13C NMR of compound 4cc

1H NMR of compound 4dc

13C NMR of compound 4dc

1H NMR of compound 4ec

13C NMR of compound 4ec

1H NMR of compound 4fc

13C NMR of compound 4fc

1H NMR of compound 4gc

13C NMR of compound 4gc

1H NMR of compound 4hc

1H NMR of compound 4hc

1H NMR of compound 4ic

13C NMR of compound 4ic

1H NMR of compound 6aa

13C NMR of compound 6aa

1H NMR of compound 6ba

13C NMR of compound 6ba

1H NMR of compound 6ca

13C NMR of compound 6ca

1H NMR of compound 6da

13C NMR of compound 6da

19F NMR of compound 6da

1H NMR of compound 6ea

13C NMR of compound 6ea

19F NMR of compound 6ea

1H NMR of compound 6fa

13C NMR of compound 6fa

1H NMR of compound 6ga

13C NMR of compound 6ga

1H NMR of compound 6ha

13C NMR of compound 6ha

1H NMR of compound 6ia

13C NMR of compound 6ia

1H NMR of compound 6ja

13C NMR of compound 6ja

1H NMR of compound 6ka

13C NMR of compound 6ka

1H NMR of compound 6la

13C NMR of compound 6la

1H NMR of compound 7a

13C NMR of compound 7a

1H NMR of compound 4qa

13C NMR of compound 4qa

1H NMR of compound 9a

13C NMR of compound 9a

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Supplementary Materials for - Science Advances · Supplementary Materials for Electrochemical oxidative oxysulfenylation and aminosulfenylation of alkenes with hydrogen evolution