Affiliation:
1. Sorbonne Université CNRS Institut Parisien de Chimie Moléculaire 4 place Jussieu 75005 Paris France
2. Université de Carthage Faculté des Sciences de Bizerte Laboratoire de Physique des Matériaux Lamellaires et Nanomatériaux Hybrides Zarzouna 7021 Bizerte Tunisie
Abstract
AbstractThe 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.