Highly regioselective coupling reactions of allylic and propargylic alcohol derivatives with gamma,gamma-dialkoxyallylic zirconium species via Zr-to-Cu transmetalation

Azusa Sato; Hisanaka Ito; Takeo Taguchi

doi:10.1021/jo0489216

Highly regioselective coupling reactions of allylic and propargylic alcohol derivatives with gamma,gamma-dialkoxyallylic zirconium species via Zr-to-Cu transmetalation

J Org Chem. 2005 Jan 21;70(2):709-12. doi: 10.1021/jo0489216.

Authors

Azusa Sato¹, Hisanaka Ito, Takeo Taguchi

Affiliation

¹ Tokyo Women's Medical University, 8-1 Kawada-cho, Shinjuku-ku, Tokyo 162-8666, Japan.

PMID: 15651826
DOI: 10.1021/jo0489216

Abstract

In the presence of CuCN, reaction of gamma,gamma-dialkoxyallylic zirconium species 4, generated in situ by treating triethyl orthoacrylate with zirconocene-butene complex, with allylic and propargylic phosphates proceeded at the alpha-position of 4 in a highly SN2'-selective manner to give the corresponding 5-alkenoates and 4,5-alkadienoates, respectively. In the present Cu(I)-mediated coupling reaction, the gamma,gamma-dialkoxyallylic zirconium species 4 serves as a synthetically useful homoenolate anion equivalent of propionate.