The authors are grateful to the National Natural Science
Foundation of China (Nos. 20625205, 20772034 and
20932002), National Basic Research Program of China
(973 Program) (No. 2011CB808603) and Doctoral Fund of
Ministry of Education of China (20090172110014) for
financial support.
Notes and references
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Scheme 2 Proposed mechanism.
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Scheme
3
Synthesis of 3ag from 1a and 2g under standard
conditions.
The reaction of 1a and methyl methacrylate (2g) was
also tested under the standard conditions. Interestingly and
surprisingly, an unexpected product 3ag was obtained in good
yield. It’s easy to understand if we write down the intermediate
B1, as there exist two b-H in the structure B1, and b-H
elimination happens selectively towards the sterically less
bulky methyl C–H giving the product 3ag (Scheme 3).
This result provided an additional proof for the proposed
mechanism in Scheme 2.
In conclusion, we have developed a new and general
protocol for the synthesis of 1-acetoxy-1,3-dienes by an acetoxy-
palladation/Heck cross-coupling/b-H elimination tandem
process. A series of 1-acetoxy-1,3-dienes were synthesized
from electron-rich and electron-deficient alkynes in high regio-
and stereoselectivity with high atom efficiency. Importantly,
the reaction used dioxygen as the terminal oxidant and H2O is
the only byproduct. Work to expand the scope and apply the
method to the field of natural products is currently underway.
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(e) Y. Shen, H. Jiang and Z. Chen, J. Org. Chem., 2010, 75, 1321.
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Org. Lett., 2009, 11, 4716; (c) C. Jonasson, A. Horva
J. Backvall, J. Am. Chem. Soc., 2000, 122, 9600.
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This journal is The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 1003–1005 1005