ORGANIC
LETTERS
2
013
Vol. 15, No. 21
531–5533
Synthesis of Dienyl Ketones via
Palladium(II)-Catalyzed Direct
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Cross-Coupling Reactions between Simple
Alkenes and Vinyl Ketones: Application to
the Synthesis of Vitamin A1 and Bornelone
†
†
†
,†
Xiang Zhang, Min Wang, Ming-Xin Zhang, Yun-He Xu,* and Teck-Peng Loh*
,†,‡
Hefei National Laboratory for Physical Sciences at the Microscale and Department of
Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui
230026, China, and Division of Chemistry and Biological Chemistry, School of Physical
and Mathematical Sciences, Nanyang Technological University, 637371, Singapore
teckpeng@ustc.edu.cn; xyh0709@ustc.edu.cn
Received September 18, 2013
ABSTRACT
An efficient and general method for the synthesis of conjugated dienyl ketones via palladium(II) acetate catalyzed direct cross-coupling between
simple alkenes and vinyl ketones is reported. This method has been successfully applied for the synthesis of Vitamin A1 and bornelone.
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Dienyl ketone fragments are basic scaffolds of many
1
olefination by a direct Wittig or HornerÀWadsworthÀ
4
Emmons reaction, transition metal catalyzed classic cou-
pling reactions, isomerization of alkynones, and others.
Among the methods, palladium and rhodium catalyzed
cross-coupling reactions have been widely utilized for the
natural products and pharmaceutically active molecules.
In addition, they are versatile synthetic building blocks in
5,6
7
2
organic synthesis. Traditional methods for the construction
of 1,3-dienyl ketone fragments involve the use of carbonyl
5,6
synthesis of dienyl ketones. However, a direct CÀC bond
formation reaction between alkenes avoiding the need to use
prefunctionalized olefins has been recognized as a more
promising method because of its atom economy and envir-
†
University of Science and Technology of China.
‡
Nanyang Technological University.
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8
onmentally friendly advantages.
While the homocoupling of two simple alkenes has been
9
reported by Gusevskaya, cross-coupling using simple
alkene has rarely been reported. In this context, our
(
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1
0
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0.1021/ol402692t r 2013 American Chemical Society
Published on Web 10/16/2013