Total synthesis of (–)-negamycin from a chiral advanced epoxide

Abstract

A concise route for the total synthesis of (–)-negamycin is described. Key point features (a) Cu-mediated ring-opening reaction of the advanced epoxide with vinyl magnesium chloride leads to the introduction of the carboxyl synthon; (b) Consecutive placement of diamino groups via azides was designed, including an unexpected cleavage of the silyl protecting group; (c) removal of four hydrogenolytically labile groups in one step.