Studies on synthesis of 1,2-cis-D-galactosides with partially benzylated intermediates

The 1-bromides of p-nitrobenzoylated 2-O-benzyl- (1) and 2,3- (8) and 2,6-di-O-benzyl-D-galactose (14) and 2-O-benzyl-D-glucose (20) were treated under Koenigs-Knorr conditions with 6-(trifluoroacetamido)-1-hexanol. Examination of the products by p.m.r. spectroscopy, g.l.c., and mass spectrometry revealed that, whereas the major product derived from 14 was the pyranoside (19), the glycosides derived from both 1 and 8 were mainly furanosides. The corresponding glycoside from 20 was entirely the pyranoside (23).