First Enantioselective Total Synthesis of (−)-Centrolobine

Abstract
The first enantioselective total synthesis of (−)-Centrolobine is described. The key reaction is the synthesis of the cis-disubstituted tetrahydropyran framework by intramolecular cyclization of the enantiopure hydroxyketone 3 with Et3SiH and TMSOTf. The stereoselective reduction of the β-ketosulfoxide 4 is the source of chirality. Revision of the absolute configuration of (−)-Centrolobine is proposed.