Gold-Catalyzed Asymmetric Intramolecular Cyclization of N-Allenamides for the Synthesis of Chiral Tetrahydrocarbolines.

Highly enantioselective gold-catalyzed intramolecular cyclization of N-allenamides was implemented by utilizing a designed chiral sulfinamide phosphine ligand (PC-Phos). This represents the first example of highly enantioselective intramolecular cyclization of N-allenamides. The practicality of this reaction was validated in the total synthesis of (R)-desbromoarborescidine A and formal synthesis of (R)-desbromoarborescidine C and (R)-deplancheine. Moreover, the catalyst system PC-Phos/AuNTf proved to be specifically efficient to promote the desymmetrization of N-allenamides in excellent yields with satisfactory ee values.