A Divergent Synthesis of l-arabino- and d-xylo-Configured Cyclophellitol Epoxides and Aziridines

A divergent synthesis to eight d‐xylo‐ and l‐arabino‐cyclophellitol and cyclophellitol aziridine derivatives is described. The syntheses start from d‐xylose and feature asymmetric allylation followed by ring‐closing metathesis as key steps. Reaction of the cyclohexenes with methyl(trifluoromethyl)dioxirane yielded the title epoxides. The aziridines were prepared either from the epimeric epoxides or by direct aziridination of the cyclohexenes. Finally, beta‐xylosylation of 2,3‐di‐O‐benzyl‐xylo‐cyclophellitol yielded the corresponding cyclitol epoxide disaccharide, thereby expanding the utility of our strategy to the synthesis of potential endoglycosidase inhibitors. A divergent synthesis to eight d‐xylo‐ and l‐arabino cyclophellitol and cyclophellitol aziridine derivatives is described. Additionally, beta‐xylosylation was accomplished with an epoxide acceptor affording the corresponding cyclitol epoxide disaccharide. These compounds serve as potential covalent glycosidase inhibitors.