Abstract
The reaction of the tert-butyldimethylsilyl protected glucal epoxide 1 with thiophenol under a variety of conditions gives three distinct adducts, including the α-phenylthioglycoside 2a, which exists both in solution and in the solid state in a 1C4 conformation in which the C-2, C-3, C-4 and C-5 substituents are all axial.