1186
T. J. Korn, P. Knochel
LETTER
Table 1 Reaction of Functionalized Aryl- and Heteroarylzinc
Halides 1 with Sulfur Monochloride, Leading to Functionalized
Organic Disulfides of Type 2
In summary, we have reported a new method for prepar-
ing functionalized disulfides using the reaction of various
functionalized aryl- and heteroarylzinc reagents with
S2Cl2. The scope and limitations of this method have been
delineated and further applications are underway.
Entry Zinc reagent of type 1 Disulfide of type 2
Yield (%)a
98b (91)c
1
Cl
ZnBr
Cl
S
2
Acknowledgment
1a
2a
We thank the Fonds der Chemischen Industrie, the Deutsche
Forschungsgemeinschaft (DFG) and Merck Research Laboratories
(MSD) for financial support. T. J. K. thanks the DFG and CNRS for
a fellowship. We also thank Chemetall GmbH (Frankfurt) and
BASF AG (Ludwigshafen) for the generous gift of chemicals.
2
3
99b
MeO
ZnBr
MeO
S
2
1b
2b
87c
References
EtO2C
ZnBr
EtO2C
S
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2
1c
2c
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Press: Oxford, 1991, 133–170.
4
5
65c
89c
PivO
ZnBr
PivO
S
2
1d
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2d
2e
CO2Et
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2
1e
6
7
62d
NC
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2
1f
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2f
63d,f
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CN
CN
S
ZnBr
2
1g
2g
2h
8
9
77d,f
EtO2C
ZnBr
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O
O
2
1h
65e
ZnBr
S
Fe
Fe
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2
1i
2i
a Yield of analytically pure product.
b Preparation of the Grignard reagent via Mg-insertion.
c Preparation of the Grignard reagent via I/Mg-exchange with i-
PrMgCl.
d Preparation of the Grignard reagent via Br/Mg-exchange with i-
PrMgCl·LiCl.
e Preparation of the lithium reagent via Sn/Li-exchange with n-BuLi.
f The crude products contained some polysulfides, which were re-
moved by recrystallization from Et2O.
Synlett 2005, No. 7, 1185–1187 © Thieme Stuttgart · New York