Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes.

Abstract

We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2 pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.