THIOACETOLYSIS REACTIONS OF 1,6-ANHYDRO-BETA-D-GLUCOPYRANOSE DERIVATIVES

Thioacetolysis of per-O-benzylated and per-O-acetylated derivatives of 1,6-anhydro-β-D-glucopyranose (1 and 3) with acetyl sulfide using acidic catalysts gave a- and 6-anomers of 1-S-acetyl-1-thio-D-glucopyranose, respectively. The formation of the β-anomer from 3 was in contrast to the predominance of the a-anomer as the product of the usual acetolysis of 3. Similar thioacetolysis of per-O-benzylated 1,6-anhydro-maltose (5) under optimized conditions resulted in opening of the 1,6-anhydro ring and simultaneous removal of the C-6 benzyl group without cleavage of the internal glycosidic linkage, giving the 6,6'α-thio-maltose derivative (6) in moderate yield. © 1990, Taylor & Francis Group, LLC. All rights reserved.