Specific C−C Bond Construction by Remote C−H Activation:  Synthesis of (−)-trans-Cembranolide

The first total synthesis of (−)-trans-cembranolide (1), isolated from Sinularia mayi Luttschw., is described. The key step in the synthesis is the diastereoselective Rh-mediated cyclization of the enantiomerically pure diazo ester 4 to the tetrahydrofuran 3a.