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advances.sciencemag.org/cgi/content/full/4/8/eaat5312/DC1
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
obtained in 80% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.27 – 7.14 (m, 8H), 4.24
(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)
calculated [M]+: 308.0638, measured: 308.0641.
(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)
calculated [M]+: 355.9637, measured: 355.9630.
(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
was obtained in 75% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.52 – 7.47 (m,
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)
calculated [M]+: 292.0689, measured: 292.0695.
(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
was obtained in 32% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.36 – 7.22 (m,
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)
calculated [M]+: 258.0845, measured: 258.0842.
1-(2-((4-Chlorophenyl)thio)-1-methoxyethyl)pyrrolidin-2-one (4pa). The desired pure product
was obtained in 61% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.33 (m,
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
obtained in 45% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.80 – 7.76 (m, 1H),
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
obtained in 74% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.38 – 7.27 (m, 7H), 7.01
– 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
obtained in 83% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.28 (m, 7H),
7.20 – 7.16 (m, 2H), 4.28 (dd, J = 8.2, 4.9 Hz, 1H), 3.28 (dd, J = 13.3, 8.2 Hz, 1H), 3.24 (s, 3H),
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
was obtained in 82% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.3 Hz,
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
F NMR (377 MHz, CDCl3): δ -62.33. HRMS: m/z (EI) calculated [M]+: 312.0796,
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
obtained in 66% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.26 (m, 6H),
7.20 – 7.09 (m, 3H), 4.31 (dd, J = 8.1, 4.9 Hz, 1H), 3.31 (dd, J = 13.2, 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 140.14, 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,
3H), 4.35 (dd, J = 8.3, 4.8 Hz, 1H), 3.33 (dd, J = 13.1, 8.3 Hz, 1H), 3.30 (s, 3H), 3.13 (dd, J = 13.1,
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,
128.15, 128.14, 126.68, 126.36, 125.74, 82.38, 57.02, 40.79, 20.42. HRMS: m/z (EI) calculated
[M]+: 258.1078, measured: 258.1089.
(2-Chlorophenyl)(2-methoxy-2-phenylethyl)sulfane (4ib). The desired pure product was
obtained in 62% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.40 – 7.28 (m, 7H),
7.21 – 7.07 (m, 2H), 4.35 (dd, J = 8.4, 4.6 Hz, 1H), 3.32 (dd, J = 13.0, 8.5 Hz, 1H), 3.26 (s, 3H),
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,
129.03, 128.60, 128.23, 127.01, 126.64, 82.37, 57.04, 40.49. HRMS: m/z (EI) calculated [M]+:
278.0532, measured: 278.0529.
(3,4-Dichlorophenyl)(2-methoxy-2-phenylethyl)sulfane (4jb). The desired pure product was
obtained in 85% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.28 (m, 7H),
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,
130.25, 129.83, 128.62, 128.33, 128.18, 126.65, 82.37, 57.01, 41.42. HRMS: m/z (EI) calculated
[M]+: 312.0142, measured: 312.0146.
(2-Methoxy-2-phenylethyl)(phenyl)sulfane (4kb).23
The desired pure product was obtained in 55%
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,
1H), 4.29 (dd, J = 7.7, 5.2 Hz, 1H), 3.32 (dd, J = 13.3, 8.2 Hz, 1H), 3.25 (s, 3H), 3.13 (dd, J = 13.3,
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,
126.90, 126.71, 83.86, 56.86, 38.62, 37.07. HRMS: m/z (EI) calculated [M]+: 258.1078, measured:
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,
13.87. HRMS: m/z (EI) calculated [M]+: 320.1002, measured: 320.1007.
(2-(2-Chloroethoxy)-2-phenylethyl)(4-chlorophenyl)sulfane (4bc). The desired pure product
was obtained in 46% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.37 – 7.21 (m,
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
obtained in 63% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.39 – 7.23 (m, 9H),
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
obtained in 63% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.37 – 7.20 (m, 9H),
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
obtained in 63% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.35 – 7.20 (m, 9H),
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
obtained in 37% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.36 – 7.28 (m, 4H),
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,
128.81, 128.27, 127.35, 126.10, 74.96, 73.38, 43.02, 28.62. HRMS: m/z (EI) calculated [M]+:
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
The desired pure product was obtained in 42%
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
was obtained in 61% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.43 – 7.27 (m,
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
product was obtained in 74% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.64 –
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,
25.40, 20.30. HRMS: m/z (EI) calculated [M]+: 367.1161, measured: 367.1164.
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
F NMR (377 MHz, CDCl3): δ -114.73. HRMS: m/z (EI) calculated [M]+: 371.0911,
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
F NMR (377 MHz, CDCl3): δ -62.42. HRMS: m/z (EI) calculated [M]+: 387.1269,
measured: 387.1259.
4-Chloro-N-(2-((4-chlorophenyl)thio)-1-phenylethyl)aniline (6fa). The desired pure product
was obtained in 56% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.41 – 7.27 (m,
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,
42.80. HRMS: m/z (EI) calculated [M]+: 373.0459, measured: 373.0466.
N-(2-((4-chlorophenyl)thio)-1-phenylethyl)-N,4-dimethylaniline (6ga). The desired pure
product was obtained in 57% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.41 –
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,
126.88, 114.14, 61.69, 36.50, 32.13, 20.29. HRMS: m/z (EI) calculated [M]+: 367.1161, measured:
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,
65.01, 39.64. HRMS: m/z (EI) calculated [M]+: 314.0644, measured: 314.0656.
N-(2-((4-chlorophenyl)thio)-1-phenylethyl)acetamide (6ia).48
The desired pure product was
obtained in 30% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.37 – 7.24 (m, 9H),
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
obtained in 52% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.40 – 7.27 (m, 9H),
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
obtained in 31% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.43 – 7.20 (m, 14H),
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
was obtained in 33% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.40 – 7.26 (m,
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
C NMR (100 MHz, CDCl3): δ
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,
1.24. HRMS: m/z (EI) calculated [M]+: 318.0845, measured: 318.0834.
(4-Chlorophenyl)(5-methoxy-2-phenylpent-2-en-1-yl)sulfane (9a). The desired pure product
was obtained in 20% yield as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.42 (d, J = 7.2 Hz,
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
C NMR (100 MHz, CDCl3): δ
141.23, 135.92, 134.75, 132.69, 132.21, 129.11, 128.88, 128.34, 127.28, 126.21, 71.85, 58.69,
34.80, 29.33. HRMS: m/z (EI) calculated [M]+: 318.0845, measured: 318.0846.
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