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Organic & Biomolecular Chemistry
Page 4 of 4
COMMUNICATION
Organic & Biomolecular Chemistry
the formation of 1,6-conjugate addition in Chart 6. On the other
hand, the less bulky L3 favors the formation of 1,4-conjugate
addition. After protonation, the desired products 3 and 4 would
be generated along with releasing the active copper catalyst for
the next catalytic cycle.
DOI: 10.1039/C9OB01086F
J. Am. Chem. Soc., 2004, 126, 84.
3
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Chart 7 Proposed mechanism
Cu/ L3 or L5
PhMe2Si-Bpin
Base
4
5
Base-Bpin
(L3 or L5)Cu-SiMe2Ph
1a
1a
A
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O
L3
Base-Bpin
O
O
PhMe2Si-Bpin
H-Base
R
OEt
OEt
Cu
OEt
PhMe2Si
PhMe2Si
Cu
O
III
OEt
H-Base
L5
R
-complex for
1,4-addition
II
-complex for
1,6-addition
Base-Cu(L3 or L5)
6
7
PhMe2Si
O
SiMe2Ph
O
O
R
OEt
OEt
R
OEt
OEt
O
3
4
Conclusions
In conclusion, we have established copper-catalyzed highly
regioselective 1,4- and 1,6-conjugate addition of silyl reagent to
the diendioates. The corresponding products were obtained in
moderate to good yields. The phosphine ligands proved to be
particularly efficient to obtain good regioselectivity of 1,4-
versus 1,6-conjugate addition to the diendioates. This work
provides a simple and general approach for the synthesis of
regioselective silylation products under mild reaction
conditions. Overall, the broad substrate scope can prove the
effective methodology for the regioselective formation of C-Si
bond.
8
9
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Conflicts of interest
“There are no conflicts to declare”.
Acknowledgments
We gratefully acknowledge the funding support of Anhui
Provincial Natural Science Foundation (1708085MB29), the
National Natural Science Foundation of China (21871240,
21672198), the Fundamental Research Funds for the Central
Universities (WK2060190082), and the State Key Program of
National Natural Science Foundation of China (21432009).
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