Stereoselective formation of alpha-alkylidene cyclic carbonates via carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide

Yoshihito Kayaki; Masafumi Yamamoto; Takao Ikariya

doi:10.1021/jo062094m

Stereoselective formation of alpha-alkylidene cyclic carbonates via carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide

J Org Chem. 2007 Jan 19;72(2):647-9. doi: 10.1021/jo062094m.

Authors

Yoshihito Kayaki¹, Masafumi Yamamoto, Takao Ikariya

Affiliation

¹ Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan.

PMID: 17221989
DOI: 10.1021/jo062094m

Abstract

Carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide (scCO2) containing P(n-C4H9)3 as a catalyst proceeded smoothly to give alpha-alkylidene-1,3-dioxolan-2-ones. Internal propargyl alcohols afforded Z-alkyl-idene cyclic carbonates exclusively. CO2 incorporation was markedly promoted under supercritical conditions, possibly due to the facile formation of a putative P(n-C4H9)3-CO2 adduct as a key intermediate.