Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric O-Alkylation with Secondary Electrophiles
摘要:
An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.
Synthesis of the 2-deoxy trisaccharide glycal of antitumor antibiotics landomycins A and E has been described. The synthesis involves an anomericO-alkylation for the synthesis of 2-deoxy beta-linked disaccharide, a tert-butyldimethylsilyl triflate-catalyzed alpha-selective L-rhodinosylation, and a lithium 4,4'-di-tert-butylbiphenyl-mediated reductive debenzylation and concomitant reductive lithiation-elimination