Total Synthesis of Brasilicardins A and C

The first total synthesis of brasilicardins A and C, novel diterpenoid saccharide amine acid hybrid metabolites with unique immunosuppressive activity, is described. The key step is a Diels-Alder/reductive angular methylation sequence capitalizing on a trans-fused bicyclic alpha-cyano-alpha,beta-enone as its precursor to construct the 8,10-dimethyltrans/syn/trans,perhydrophenanthierie skeleton. Other notable features include an,anti selective aldol reaction, a stereocontrolled glycosylation of a C2 alcohol, and a one-pot, two-step global deprotection sequence that did not damage these sensitive molecules.