The Chan-Lam reaction of chalcogen elements leading to aryl chalcogenides

Article abstract of DOI:10.1002/adsc.201300853

A copper-catalyzed chalcogenation of arylboronic acids with elemental sulfur or selenium is established, which provides diaryl disulfides or diaryl monoselenides in moderate to good yields with excellent selectivities, respectively. Moreover, after sequential reduction and coupling with aryl/alkyl iodides in one pot, unsymmetrical monosulfides were obtained in good yields.

Full text of DOI:10.1002/adsc.201300853

Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013

Supporting Information
The Chan-Lam Reaction of Chalcogen Elements Leading to
Aryl Chalcogenides
Jin-Tao Yu,* Huan Guo, Yuanqiuqiang Yi, Haiyang Fei, Yan Jiang
School of Petrochemical Engineering, Jiangsu Province Key Laboratory of Fine
Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. China;
yujintao@cczu.edu.cn
Table of Contents
1. General information ..............................................................................................S2
2. Synthetic procedures..............................................................................................S2
3. Characterization data for the products ...............................................................S3
4. References...............................................................................................................S8
5. Copies of the 1H NMR and 13C NMR spectra......................................................S9
6. GC-MS analysis of the coupling compounds.....................................................S34
S1

1. General information
All chemicals were used as received without further purification unless stated
otherwise. 1H NMR and 13C NMR spectra were recorded at ambient temperature on a
300 MHz NMR spectrometer (75 MHz for 13C). NMR experiments are reported in δ
units, parts per million (ppm), and were referenced to CDCl3 ( 7.26 or 77.0 ppm) as
the internal standard. The coupling constants J are given in Hz. Column
chromatography was performed using EM Silica gel 60 (300-400 mesh).
2. Synthetic procedures
General procedure for the synthesis of aryl sulfides/selenides: Under N2, the
mixture of arylboronic acid (0.4 mmol), sulfur/selenium powder (0.8 mmol), CuF2 (10
o
mol %) in Py/DMSO (2 mL, 2 : 1) was stirred under 100 C for 12 h. After the
completion of the reaction (monitored by TLC), the solvent was concentrated in
vacuum and the residue was purified by flash column chromatography on silica gel
with petroleum ether-EtOAc as the eluent to give the desired product.
General procedure for the synthesis of aryl thiols: Under N2, the mixture of
arylboronic acid (0.4 mmol), sulfur powder (0.8 mmol), CuF2 (10 mol %) in
o
Py/DMSO (2 mL, 2 : 1) was stirred at 100 C for 12 h. To this reaction mixture,
NaBH4 (1 mmol) was added. After the resultant reaction solution was stirred at 40 oC
for 5 h, water was added to quench the reaction. The mixture was extracted with ethyl
acetate, and the combined organic layer was washed with H2O and brine, dried over
Na2SO4. The solvent was concentrated in vacuum and the residue was purified by
flash column chromatography on silica gel to give the desired product.
General procedure for the synthesis of unsymmetrical monosulfides: Under N2,
the mixture of arylboronic acid (0.4 mmol), sulfur powder (0.8 mmol), CuF2 (10 mol
%) in Py/DMSO (2 mL, 2 : 1) was stirred at 100 oC for 12 h. To this reaction mixture,
S2

NaBH4 (1 mmol) was added. After the resultant reaction solution was stirred at 40 oC
for 5 h, aryl/alkyl iodide (0.6 mmol) was added and stirred at 100 oC for another 20 h.
The reaction mixture was extracted with ethyl acetate. The organic layer was washed
with H2O and brine, dried over Na2SO4. After removal of the solvent in vacuum, the
residue was purified by flash column chromatography on silica gel to give the desired
unsymmetrical monosulfides.
3. Characterization data for the products
dis(4-methylphenyl) disulfide (2a)[1]
White solid (46.3 mg, 94% yield). 1H NMR (CDCl3, 300 MHz): δ 7.39 (d, J = 8.2 Hz,
13
4H), 7.11 (d, J = 8.0 Hz, 4H), 2.32 (s, 6H); C NMR (CDCl3, 75 MHz): δ 137.4,
133.8, 129.8, 128.5, 21.1.
diphenyl disulfide (2b)[1]
White solid (41.4 mg, 95% yield). 1H NMR (CDCl3, 300 MHz): δ 7.55-7.53 (m, 4H),
13
7.36-7.27 (m, 4H), 7.25-7.23 (m, 2H). C NMR (CDCl3, 75 MHz): δ 136.9, 129.0,
127.4, 127.1.
bis(3-methylphenyl) disulfide (2c)[2]
White solid (34.9 mg, 71% yield). 1H NMR (CDCl3, 300 MHz): δ 7.48 (s, 4H), 7.32 (t,
J = 7.6 Hz, 2H), 7.16 (d, J = 7.5 Hz, 2H); 13C NMR (CDCl3, 75 MHz): δ 138.7, 136.8,
128.7, 127.9, 124.4, 21.2.
bis(4-methoxyphenyl) disulfide (2d)[1]
S3

White solid (52.8 mg, 95% yield). 1H NMR (CDCl3, 300 MHz): δ 7.40 (d, J = 8.9 Hz,
4H), 6.84 (d, J = 8.8 Hz, 4H), 3.80 (s, 6H). 13C NMR (CDCl3, 75 MHz): δ 159.9,
132.7, 128.4, 114.6, 55.4.
bis(2-methoxyphenyl) disulfide (2e)[3]
White solid (36.1 mg, 65% yield). 1H NMR (CDCl3, 300 MHz): δ 7.53 (d, J = 7.7 Hz,
13
2H), 7.19 (t, J = 7.5 Hz, 2H), 6.93-6.84 (m, 4H), 3.90 (s, 6H). C NMR (CDCl3, 75
MHz): δ 159.2, 129.2, 128.0, 120.4, 118.4, 117.1, 55.3.
bis(4-chlorophenyl) disulfide (2f)[1]
White solid (51.5 mg, 90% yield). 1H NMR (CDCl3, 300 MHz): δ 7.40 (d, J = 8.6 Hz,
4H), 7.29 (d, J = 8.7 Hz, 4H). 13C NMR (CDCl3, 75 MHz): δ 135.0, 133.6, 129.3
(One carbon is invisible because of overlapping.).
bis(2-chlorophenyl) disulfide (2g)[1]
White solid (53.8 mg, 94% yield). 1H NMR (CDCl3, 300 MHz): δ 7.55 (d, J = 7.9 Hz,
2H), 7.37 (d, J = 7.6 Hz, 2H), 7.16-7.23 (m, 4H). 13C NMR (CDCl3, 75 MHz): δ
134.4, 131.8, 129.7, 127.8, 127.6, 127.2.
bis(4-bromophenyl) disulfide (2h)[4]
White solid (63.6 mg, 85% yield). 1H NMR (CDCl3, 300 MHz): δ 7.43 (d, J = 8.6 Hz,
13
4H), 7.33 (d, J = 8.6 Hz, 4H). C NMR (CDCl3, 75 MHz): δ 135.7, 132.2, 129.4,
S4

121.5.
bis(4-fluophenyl) disulfide (2i)[4]
S S
F
F
1
White solid (40.6 mg, 80% yield). HNMR (CDCl3, 300MHz): δ 6.95-6.89 (m, 2H),
13
6.80-6.75 (m, 2H), 0.25 (s, 9H); CNMR (CDCl3, 75MHz): δ 163.0 (d, JC-F = 245.7
Hz), 133.2 (d, JC-F = 8.4 Hz), 131.2 (d, JC-F = 8.3 Hz), 116.2 (d, JC-F = 23.3 Hz).
bis(4-cyanophenyl) disulfide (2j)[6]
White solid (36.4 mg, 68% yield). 1H NMR (CDCl3, 300 MHz): δ 7.61 (d, J = 8.8 Hz,
13
4H), 7.55 (d, J = 8.8 Hz, 4H); C NMR (CDCl3, 75 MHz): δ 142.1, 132.8, 126.5,
117.9, 110.9.
bis(4-(trifluoromethyl)phenyl) disulfide (2k)[6]
1
White solid (31.9 mg, 45% yield). H NMR (CDCl3, 300 MHz): δ 7.60-7.26 (m,
8H).13C NMR (CDCl3, 75 MHz): δ 140.8, 129.8, 128.4, 126.6, 123.8 (JC-F = 270 Hz).
bis(2-naphthyl phenyl) disulfide (2l)[1]
1
White solid (53.4 mg, 84% yield). H NMR (CDCl3, 300 MHz): δ 7.99 (s, 2H),
7.80-7.72 (m, 6H), 7.64-7.60 (m, 2H), 7.49-7.42 (m, 4H); 13C NMR (CDCl3, 75 MHz)
δ 134.3, 133.3, 131.0, 129.9, 129.2, 128.9, 127.8, 127.6, 127.3, 127.1.
di(4-methylphenyl) selenide (4a)[7]
S5

White solid (44.5 mg, 85% yield). 1H NMR (CDCl3, 300 MHz): δ 7.38 (d, J = 8.1 Hz,
13
4H), 7.10 (d, J = 7.8 Hz, 4H), 2.34 (s, 6H); C NMR (CDCl3, 75 MHz): δ 137.2,
132.9, 130.1, 127.7, 21.1.
diphenyl selenide (4b)[7]
White solid (34.2 mg, 73% yield). 1H NMR (CDCl3, 300 MHz): δ 7.63-7.59 (m, 4H),
7.29-7.25 (m, 6H). 13C NMR (CDCl3, 75 MHz): δ 132.8, 131.5, 129.1, 127.6.
di(4-methoxyphenyl) selenide (4c)[7]
1
White solid (46.5 mg, 79% yield). H NMR (CDCl3, 300 MHz): 7.40 (d, J = 8.8 Hz,
13
4H), 6.81 (d, J = 8.8 Hz, 4H), 3.79 (s, 6H); C NMR (CDCl3, 75 MHz): δ 159.2,
134.6, 122.1, 115.0, 55.3.
di(4-chlorophenyl) selenide (4d)[7]
1
White solid (51.3 mg, 83% yield). H NMR (CDCl3, 300 MHz): 7.38 (d, J = 8.5 Hz,
13
4H), 7.25 (d, J = 8.4 Hz, 4H); C NMR (CDCl3, 75 MHz): δ 134.3, 133.9, 129.6,
129.0.
di(2-chlorophenyl) selenide (4e)[8]
White solid (50.1 mg, 83% yield). 1H NMR (CDCl3, 300 MHz): δ 7.62-7.59 (m, 4H),
13
7.35-7.32 (m, 2H), 7.18-7.15 (m, 2H); C NMR (CDCl3, 75 MHz): δ. 133.2, 130.7,
129.3, 129.1, 128.4, 127.9.
di(4-bromophenyl) selenide (4f)[7]
S6

White solid (49.9 mg, 64 % yield). 1H NMR (CDCl3, 300 MHz): δ 7.40 (d, J = 8.6 Hz,
13
4H), 7.30 (d, J = 8.6 Hz, 4H); C NMR (CDCl3, 75 MHz): δ 134.6, 132.6, 129.6,
122.0.
4-methylbenzenethiol (5a)[9]
White solid (39.2 mg, 79% yield). 1H NMR (CDCl3, 300 MHz): δ 7.19 (d, J = 8.0 Hz,
2H), 7.05 (d, J = 8.0 Hz, 2H), 3.39 (s, 1H), 2.30 (s, 3H). 13C NMR (CDCl3, 75 MHz):
δ 135.1, 129.8, 129.7, 126.5, 21.0.
benzenethiol (5b)[9]
1
Colorless liquid (35.2 mg, 80% yield). H NMR (CDCl3, 300 MHz): δ 7.27-7.10 (m,
5H), 3.43 (s, 1H); 13C NMR (CDCl3, 75 MHz): δ 130.7, 129.3, 129.0, 125.5.
4-chlorobenzenethiol (5c)[9]
1
White solid (46.6 mg, 81% yield). H NMR (CDCl3, 300 MHz): δ 7.20 (s, 4H), 3.45
(s, 1H). 13C NMR (CDCl3, 75 MHz): δ 131.7, 130.7, 129.1, 129.1.
4-bromobenzenethiol (5d)[10]
White solid (59.7 mg, 79% yield). 1H NMR (CDCl3, 300 MHz): δ 7.35 (d, J = 8.5 Hz,
13
2H), 7.14 (d, J = 8.5 Hz, 2H), 3.44 (s, 1H); C NMR (CDCl3, 75 MHz): δ 132.1,
131.0, 129.9, 119.4.
4-methoxyphenyl 4-methylphenyl sulfide (3ab)[11]
Colorless oil (73.6 mg, 80% yield). 1H NMR (CDCl3, 300 MHz): δ 7.42 (d, J = 8.9 Hz,
2H), 7.23 (d, J = 8.3 Hz, 2H), 7.11 (d, J = 8.1 Hz, 2H), 6.90 (d, J = 8.9 Hz, 2H), 3.83
S7

(s, 3H), 2.35 (s, 3H). 13C NMR (CDCl3, 75 MHz): δ 159.4, 136.0, 134.3 (2C), 134.2,
129.7 (2C), 129.3 (2C), 125.5, 114.8 (2C), 55.2, 20.9.
4-chlorophenyl phenyl sulfide (3bc)[11]
S
Cl
Colorless oil (68.6 mg, 78% yield). 1H NMR (CDCl3, 300 MHz): δ 7.38-7.26 (m, 8H).
13C NMR (CDCl3, 75 MHz): δ 135.1, 134.6, 132.9, 132.0, 131.3, 129.3, 129.3, 127.4.
4-chlorophenyl methyl sulfide (3cd)[12]
Colorless oil (48.7 mg, 77% yield). 1H NMR (CDCl3, 300 MHz): δ 7.24 (d, J = 8.7 Hz,
13
2H), 7.16 (d, J = 8.7 Hz, 2H), 2.46 (s, 3H). C NMR (CDCl3, 75 MHz): δ 136.9,
130.7, 128.8, 127.7, 15.9.
4. References
[1] R. Kumar, N. Sharma, U. K. Sharma, A. Shard, A. Sinha, Adv. Synth. Catal. 2012, 354, 2107.
[2] M. Carril, R. SanMartin, E. Domínguez, I. Tellitu, Green Chem. 2007, 9, 315.
[3] J. L. G. Ruano, A. Parra, J. Alemán, Green Chem. 2008, 10, 706.
[4] D. R. Dreyer, H.-P. Jia, A. D. Todd, J. Geng, C. W. Bielawski, Org. Biomol. Chem. 2011, 9,
7292.
[5] Q. Yang, J. Hu, Patent CN 101386589 B, 2008.
[6] M. Oba, K. Tanaka, K. Nishiyama,W. Ando, J. Org. Chem. 2011, 76, 4173.
[7] N. Taniguchi, Tetrahedron 2012, 68, 10510.
[8] Y. Li, C. Nie, H. Wang, X. Li, F. Verpoort, C. Duan, Eur. J. Org. Chem. 2011, 76, 7331.
[9] H.-J. Xu, Y.-F. Liang, Z.-Y. Cai, H.-X. Qi, C.-Y. Yang, Y.-S. Feng, J. Org. Chem. 2011, 76,
2296.
[10] Y. Jiang, Y. Qin, X. Zhang, J. Dong, D. Ma, Org. Lett. 2009, 11, 5250.
[11] M. A. Fernández-Rodríguez, J. F. Hartwig, J. Org. Chem. 2009, 74, 1663.
[12] A. McCurdy, L. Jimenez, D. A. Stauffer, D. A. Dougherty, J. Am. Chem. Soc. 1992, 114,
10314.
S8

5. Copies of the 1H NMR and 13C NMR spectra
S
S
Me
Me
2a
S9

S
S
2b
S10

Me
S
S
Me
2c
S11

S
S
MeO
OMe
2d
S12

OMe
OMe
S
S
2e
S13

S
S
Cl
Cl
2f
S14

Cl
Cl
S
S
2g
S15

S
S
Br
Br
2h
S16

S
S
F
F
2i
S17

S
S
NC
CN
2j
S18

S
S
F3C
CF3
2k
S19

S
S
2l
S20

Se
Me
Me
4a
S21

Se
4b
S22

Se
MeO
OMe
4c
S23

Se
Cl
Cl
4d
S24

Cl
Cl
Se
4e
S25

Se
Br
Br
4f
S26

SH
Me
5a
S27

SH
5b
S28

SH
Cl
5d
S29