Large Scale Epoxide Opening by a Pendant Silanol

Abstract

Abstract This chapter presents the procedure for the large scale epoxide opening by a pendant silanol. It focuses on the development of the di‐tert butyl silanol functional group into a synthetically useful auxiliary. Silanols only sporadically appeared in the organic synthesis literature. Silanols are excellent directing groups for Pd‐catalyzed C–H functionalization reaction. A gold‐catalyzed cyclization of silanols is developed onto pendant alkynes; these heterocycles serve as versatile precursors for Mukaiyama‐type aldol condensations. Alkenyl silanols readily cyclize into dioxasilinane organomercury compounds. As epoxides are very versatile and ubiquitous intermediates in organic synthesis, a silanol‐tethered ring opening of epoxides is developed as a first step in this direction.