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1347
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3aa (<3%)
PhSCu (1.2 equiv)
KI (20 mol%)
route b
Cs2CO3 (1 equiv), N2
DMSO, 80 oC, 4h
Ph
Ph
CuI (20 mol%)
Cs2CO3 (1 equiv)
DMSO, 80 oC, 24h
NH
Cs2CO3 (1 equiv)
DMSO, 80 oC, 4h
No reaction
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route d
route c
NH2
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1a
PhSCu (1.2 equiv)
KI (20 mol%)
2a
, CuI, Cs
DMSO, 80
route a
r
oute e
52%
Cs2CO3, Air
DMSO, 80 oC, 4 h
2
CO
C, 4h
o
,
29%
3
SPh
CuI (1 equiv), N2
Cs2CO3 (1 equiv)
1a + 2a
DMSO, 80 oC, 4h
route f, 40%
Ph
N
H
3aa
Scheme 2. Preliminary study on the formation pathway of 3.
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R
E
ER
Cs2CO3
R1
R1
1
NH2
NH
(IV)
(III)
RECu
RE ER
3
(II)
Cu
I
(I)
12. (a) Wasilke, J. C.; Obrey, S. J.; Baker, R. T.; Bazan, G. C. Chem. Rev. 2005, 105,
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I-, O2
(RE)2
CuI
E = S, Se
2
2
Scheme 3. Plausible mechanism for copper-catalyzed chalcogenoami-nation of
2-alkynylanilines with dichalcogenides.
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Acknowledgments
We thank the NNSF of China, 973 Program (2009CB825300),
Shanghai Science and Technology Committee (No. 08dj1400100),
the Research Fund for the Doctoral Program of Higher Education
of China, and Shanghai Leading Academic Discipline Project for
financial support (B108).
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2006, 71, 7874; (c) Takeuchi, H.; Hiyama, T.; Kamai, N.; Oya, H. J. Chem. Soc.,
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Supplementary data
21. General procedure for synthesis of 3-chalcogenylindoles:
A mixture of 2-
Supplementary data associated with this article can be found, in
Alkynylaniline (0.2 mmol), dichalcogenide (0.15 mmol), CuI (0.02 mmol), and
Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air
atmosphere. After completion of the reaction that was monitored by GC–MS
or TLC, 25 mL water was added, and the mixture was extracted with ethyl
acetate, the combined organic layers were washed with water (10 mL ꢂ 3),
dried over anhydrous Na2SO4. After filtration and removal of solvents in
vacuum, the residue was purified by silica gel column chromatography to
afford the corresponding products.
References and notes
1. For reviews on indole chemistry, see: (a) Sundberg, R. L. Indoles; Academic:
London, 1996; (b) Katritzky, A. R.; Pozharskii, A. F. Handbook of Heterocyclic