Gold(III) Chloride and Phenylacetylene: A Catalyst System for the Ferrier Rearrangement, and <i>O</i>‐Glycosylation of 1‐<i>O</i>‐Acetyl Sugars as Glycosyl Donors

Abstract

Abstract We have developed a new catalyst system comprising AuCl 3 and phenylacetylene that promotes the Ferrier rearrangement of glycals and 2‐acetoxymethylglycals with different nucleophiles, and also the O ‐glycosylation of 1‐ O ‐acetyl sugars to obtain a variety of useful glycosides at room temperature through relay catalysis. Good anomeric selectivity was observed for the Ferrier rearrangements, whereas the O ‐glycosylation of 1‐ O ‐acetyl sugars gave mixtures of diastereomers with moderate to excellent selectivity.