Electrophilic interaction of 2,3-allenoates with PhSeCl. An unexpected highly stereoselective synthesis of 3-phenylseleno-4-oxo-2(E)-alkenoates

Guofei Chen; Chunling Fu; Shengming Ma

doi:10.1021/jo061680c

Electrophilic interaction of 2,3-allenoates with PhSeCl. An unexpected highly stereoselective synthesis of 3-phenylseleno-4-oxo-2(E)-alkenoates

J Org Chem. 2006 Dec 22;71(26):9877-9. doi: 10.1021/jo061680c.

Authors

Guofei Chen¹, Chunling Fu, Shengming Ma

Affiliation

¹ Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, PR China.

PMID: 17168613
DOI: 10.1021/jo061680c

Abstract

We have previously reported an efficient synthesis of beta-phenylselenium-substituted butenolides via electrophilic cyclization of 2,3-allenoates with PhSeCl in aqueous MeCN. However, when 2,3-allenoates were treated with PhSeCl in MeCN, 3-phenylseleno-4-oxo-2(E)-alkenoates were formed unexpectedly. The addition of Li2CO3 improved the yield and the selectivity of the reaction. A possible mechanism involving a decomposition of selenate esters was proposed.