Stereoselective Synthesis of 4‐Hydroxy‐1‐Silyl‐1‐Allenylboranes and Access to 2‐Silylethynyl‐1,3‐Diols

Abstract

The highly stereoselective gem‐silylboration of chiral 2‐substituted 1‐ethynylepoxides is reported herein. The reaction involves first the deprotonation of the epoxides in the acetylenic position followed by transmetallation with Et3SiBpin. The transient silylborane ate‐complexes generated undergo the stereoselective 1,2‐migration of the Et3Si‐group to the sp‐hybridized terminus carbon of the ethynyl‐moiety in a stereospecific anti‐addition. The moisture‐sensitive and thermally unstable 4‐hydroxy‐1‐triethylsilyl‐1‐allenyl(pinacolato)boranes thus obtained react with aldehydes through an SE2’‐mode of addition, affording highly functionalized 2‐triethysilylethynyl‐1,3‐diols with a good diastereoselectivity which is rationalized by a Yamamoto‐Houk type transition state model.