Cu-Catalyzed Selective Synthesis of Diaryl Chalcogenides
1-[4-(Phenylthio)phenyl]ethanone (3e): The crude product obtained
by the General Procedure was purified on a silica gel column with
ethyl acetate/petroleum ether (1:50) to give a slightly yellow solid in
60% yield (0.068 g) or 64% yield (0.073 g) when 1-(4-bromophen-
yl)ethanone was employed. CAS: 10169-55-8. 1H NMR (400 MHz,
[1]Benzothieno[3,2-b]benzothiophene (4b): The crude product ob-
tained by the General Procedure was purified on a silica gel column
with petroleum ether to give a white solid in 61% yield (0.0293 g).
1
CAS: 248-70-4; m.p. 219–219.7 °C. H NMR (400 MHz, CDCl3):
δ = 7.92–7.87 (m, 4 H, Ar-H), 7.47–7.38 (m, 4 H, Ar-H) ppm. 13C
CDCl3): δ = 7.81 (d, J = 8.4 Hz, 2 H, Ar-H), 7.50–7.47 (m, 2 H, NMR (100 MHz, CDCl3): δ = 142.6, 133.7, 133.4, 125.2, 125.1,
Ar-H), 7.41–7.38 (m, 3 H, Ar-H), 7.20 (d, J = 8.4 Hz, 2 H, Ar-H),
2.54 (s, 3 H, COCH3) ppm. 13C NMR (100 MHz, CDCl3): δ =
197.2, 145.0, 134.5, 134.0, 132.1, 129.8, 129.0, 128.9, 127.5,
26.6 ppm. GC-MS (EI): m/z = 228 [M]+.
124.2, 121.8 ppm. GC-MS (EI): m/z = 240 [M]+.
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, characterization data and copies of
1
the original H NMR and 13C NMR spectra of all compounds.
(4-Nitrophenyl)(phenyl)sulfane (3f): The crude product obtained by
the General Procedure was purified on a silica gel column with
ethyl acetate/petroleum ether (1:50) to give a yellow oil in 78% yield
(0.090 g) or 80% yield (0.092 g) when 1-bromo-4-nitrobenzene was
Acknowledgments
1
This work was supported by the National Natural Science Founda-
tion of China (NSFC) (Project Numbers 20876021 and 20923006)
and the Education Department of Liaoning Province (2009S021).
employed. CAS: 952-97-6. H NMR (400 MHz, CDCl3): δ = 8.04
(d, J = 8.8 Hz, 2 H, Ar-H), 7.55–7.52 (m, 2 H, Ar-H), 7.46–7.44
(m, 3 H, Ar-H), 7.16 (d, J = 9.2 Hz, 2 H, Ar-H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 148.6, 145.4, 134.8, 130.4, 130.1, 129.8,
126.7, 124.1 ppm. GC-MS (EI): m/z = 231 [M]+.
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(4-Chlorophenyl)(4-nitrophenyl)sulfane (3g): The crude product ob-
tained by the General Procedure was purified on a silica gel column
with ethyl acetate/petroleum ether (1:50) to give a yellow solid in
71% yield (0.094 g). CAS: 21969-11-9. 1H NMR (400 MHz,
CDCl3): δ = 8.07 (d, J = 8.8 Hz, 2 H, Ar-H), 7.48–7.40 (m, 4 H,
Ar-H), 7.18 (d, J = 9.2 Hz, 2 H, Ar-H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 147.7, 145.7, 136.1, 135.9, 130.4, 129.2, 127.0,
124.2 ppm. GC-MS (EI): m/z = 265 [M]+, 267 [M + 2]+.
(4-Methoxyphenyl)(4-nitrophenyl)sulfane (3h): The crude product
obtained by the General Procedure was purified on a silica gel col-
umn with ethyl acetate/petroleum ether (1:50) to give a yellow solid
in 79% yield (0.103 g). CAS: 22865-50-5. 1H NMR (400 MHz,
CDCl3): δ = 8.02 (d, J = 8.8 Hz, 2 H, Ar-H), 7.48 (d, J = 8.8 Hz,
2 H, Ar-H), 7.08 (d, J = 8.8 Hz, 2 H, Ar-H), 6.99 (d, J = 8.8 Hz,
2 H, Ar-H), 3.86 (s, 3 H, OCH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 161.2, 150.2, 145.0, 137.2, 125.6, 124.0, 120.1, 115.8,
55.6 ppm. GC-MS (EI): m/z = 261 [M]+.
(4-Nitrophenyl)(p-tolyl)sulfane (3i): The crude product obtained by
the General Procedure was purified on a silica gel column with
ethyl acetate/petroleum ether (1:50) to give a yellow solid in 85%
[3] a) J. Lindley, Tetrahedron 1984, 40, 1433–1456; b) A. Osuka,
N. Ohmasa, H. Suzuki, Synthesis 1982, 857–858.
1
yield (0.104 g). CAS: 22865-48-1. H NMR (400 MHz, CDCl3): δ
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3220; b) A. W. Thomas, S. V. Ley, Angew. Chem. 2003, 115,
5558; Angew. Chem. Int. Ed. 2003, 42, 5400–5449; c) I. P. Belet-
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I. P. Beletskaya, V. P. Ananikov, Chem. Rev. 2011, 111, 1596–
1636; e) J. P. Stambuli, C. C. Eichman, Molecules 2011, 16,
590–608.
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B. Chabaud, R. Labaudiniere, H. Christol, Organometallics
1985, 4, 657–661; b) V. Percec, J. Y. Bae, D. H. Hill, J. Org.
Chem. 1995, 60, 6895–6903.
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Shimizu, Y. Asami, J. Shiobara, Y. Kato, M. Kosugi, Bul.
Chem. Soc. Jpn. 1980, 53, 1385–1389; b) I. P. Beletskaya, A. S.
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= 8.02 (d, J = 7.6 Hz, 2 H, Ar-H), 7.42 (d, J = 6.8 Hz, 2 H, Ar-
H), 7.25 (d, J = 7.6 Hz, 2 H, Ar-H), 7.11 (d, J = 7.6 Hz, 2 H, Ar-
H), 2.40 (s, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ =
149.4, 145.2, 140.3, 135.2, 130.9, 126.5, 126.2, 124.0, 21.4 ppm.
GC-MS (EI): m/z = 245 [M]+.
(4-Chlorophenyl)(4-methoxyphenyl)sulfane (3j): The crude product
obtained by the General Procedure was purified on a silica gel col-
umn with ethyl acetate/petroleum ether (1:50) to give a white solid
in 78% yield (0.098 g). CAS: 20912-69-0. 1H NMR (400 MHz,
CDCl3): δ = 7.39 (d, J = 8.8 Hz, 2 H, Ar-H), 7.17 (d, J = 8.8 Hz,
2 H, Ar-H), 7.06 (d, J = 8.4 Hz, 2 H, Ar-H), 6.89 (d, J = 8.8 Hz,
2 H, Ar-H), 3.80 (s, 3 H, OCH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 160.2, 137.5, 135.7, 131.7, 129.4, 129.1, 123.8, 115.2,
55.5 ppm. GC-MS (EI): m/z = 250 [M]+, 252 [M + 2]+.
2-Phenylbenzo[b]thiophene (4a): The crude product obtained by the
General Procedure was purified on a silica gel column with petro-
leum ether to give a white solid in 99% yield (0.0416 g). CAS: 1207-
95-0; m.p. 174.8–175.3 °C. 1H NMR (400 MHz, CDCl3): δ = 7.82–
7.70 (m, 4 H, Ar-H), 7.53 (s, 1 H, Ar-H), 7.43–7.28 (m, 5 H, Ar-
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.4, 140.9, 139.7,
134.5, 129.1, 128.4, 126.7, 124.7, 124.5, 123.7, 122.4, 119.6 ppm.
GC-MS (EI): m/z = 210 [M]+.
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a) F. Y. Kwong, S. L. Buchwald, Org. Lett. 2002, 4, 3517–3520;
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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