Cyanoesterification of 1,2-Dienes:  Synthesis and Transformations of Highly Functionalized α-Cyanomethylacrylate Esters

Yoshiaki Nakao,* Yasuhiro Hirata, and Tamejiro Hiyama*;
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
J. Am. Chem. Soc., 2006, 128 (23), pp 7420–7421
DOI: 10.1021/ja0606834
Publication Date (Web): May 12, 2006
Copyright © 2006 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, nakao@npc05.kuic.kyoto-u.ac.jp, ; , thiyama@npc05.kuic.kyoto-u.ac.jp

Abstract

Abstract Image

A Ni/PMe2Ph catalyst is found to effect regioselective addition of cyanoformate esters across 1,2-dienes, giving rise to 3-alkoxycarbonyl-3-butenenitriles. Functional groups such as cyano, protected hydroxyl, and amino groups in the 1,2-diene substrates are tolerated. Isomerization of the initial products to thermodynamically more stable isomers takes place possibly through further oxidative addition of the C−CN bond of 3-alkoxycarbonyl-3-butenenitriles to Ni(0) followed by reductive elimination. The cyanoesterification products undergo further addition across alkynes in the presence of a Ni/P(4-CF3−C6H4)3 catalyst.

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History

  • Published In Issue June 14, 2006
  • Received January 29, 2006

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