Total Synthesis and Structural Revision of Mangrolide D.

The unique 18-membered macrocyclic natural product mangrolide D was prepared in totally synthetic form. Key steps feature an Au-catalyzed glycosylation, aza-Michael addition, and LaLi3tris(binaphthoxide) catalyzed epoxidation. Detailed analysis of the constitution and configuration of the carbohydrate segment and the total synthesis of the revised structure led to structural revision of the originally proposed structure.