Total Synthesis of the Antibiotic Kendomycin: A Macrocyclization Using the Tsuji-Trost Etherification.

A highly stereocontrolled, convergent total synthesis of kendomycin [(−)-TAN2162], an ansa-macrocyclic antibiotic, is reported. The key of the strategy is an unprecedented Tsuji-Trost macrocyclic etherification, followed by a transannular Claisen rearrangement to construct the 18-membered carbocyclic framework. The oxa-six- and five-membered rings were also stereoselectively constructed respectively by a cascade oxidative cyclization at an unfunctionalized benzylic position and using a one-pot epoxidation/5- exo-tet epoxide opening. [ABSTRACT FROM AUTHOR]