SFox imidates as versatile glycosyl donors for chemical glycosylation

Abstract

Described herein is a continuation of our studies dedicated to the development of novel classes of leaving groups based on O- and S-imidates. The main focus of the study presented herein is the synthesis of novel 3,3-difluoro-3H-indol-2-ylthio (SFox) imidates and their application as glycosyl donors in chemical glycosylation. Being thioimidates, these compounds are more stable than O-imidates albeit much more reactive than conventional alkyl/arylthio glycosides. This study demonstrates that SFox imidates can be activated either with soft thiophilic reagents (N-iodosuccinimide or transition metal salts), typical for the activation of thioglycosides or thioimidates, or hard electrophilic reagents (protic or Lewis acids) common for the activation of O-imidates. Expectedly, complete β-selectivity was obtained from SFox donors equipped with 2-O-benzoyl group. Surprisingly, complete α-selectivity was obtained from 2-O-benzylated SFox imidates in all investigated cases.