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Synlett 2010(12): 1833-1836  
DOI: 10.1055/s-0030-1258093
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Double α-Addition Reaction of ortho-Hydroxyacetophenones to Ethyl Propiolates Mediated by Ph3P: Synthesis of Functionalized 1,4-Pentadienes

Ling-Guo Mengb, Kai Tangb, Hui-Fang Liua, Jiang Xiaoa, Song Xue*a
a Department of Applied Chemistry, Tianjin University of Technology, Tianjin 300191, P. R. of China
Fax: +86(22)60214252; e-Mail: xuesong@ustc.edu.cn;
b Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. of China
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Publication History

Received 9 April 2010
Publication Date:
14 June 2010 (online)

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Abstract

A new way of synthesizing functionalized 1,4-pentadienes by double α-addition reaction of ortho-hydroxyaceto­phenones to ethyl propiolate mediated by Ph3P in moderate yields is described. On the other hand, other ortho-hydroxyphenyl ketones resulted in the single α-addition products in moderate to good yields.

Key words

α-addition - functionalized 1,4-pentadienes - Ph3P - ortho-acylphenols - ethyl propiolates

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General Reaction Procedure
To a solution of ortho-acylphenols (0.6 mmol) with terminal alkynoates (0.6 mmol) in dry CH2Cl2 (2 mL) was added Ph3P (79 mg, 0.3 mmol), and the resulting mixture was stirred at r.t. for 16 h. The solvent was removed in vacuo, and the residue was purified by column chromatography on silica gel (PE-EtOAc = 20:1) to give the desired product.