Thiosilanes in sulfur chemistry: A general approach to silyl thiaheterocycles and their use in stereoselective synthesis

Abstract

Abstract 2‐Silyl five‐membered sulfurated heterocycles can be efficiently accessed through reaction of bromo(methoxy)methyl trimethylsilane with suitable β‐substituted mercaptans HS‐CH 2 CH 2 ‐XH, leading to the formation of 2‐silyl‐1,3‐dithiols, 2‐silyl‐1,3‐thiazolidines, and 2‐silyl‐1,3‐oxathiolanes. β‐Mercaptoalcohols are obtained through regioselective ring opening of epoxides with bis(trimethylsilyl)sulfide (HMDST). In a similar way, thiiranes and aziridines react with HMDST, leading to the formation of 1,2‐dithiols and β‐aminothiols. Fluoride ion induced functionalization of the pentaatomic heterocycles smoothly affords the transfer of the heterocyclic ring on electrophiles, thus showing these silyl derivatives as a new class of acyl anion equivalents. When stereodefined compounds are reacted, the stereoinformation is transferred from the carbon–silicon to the newly formed carbon–carbon bond. © 2007 Wiley Periodicals, Inc. 18:516–526, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20345