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

Abstract 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 2 proved to be specifically efficient to promote the desymmetrization of N‐allenamides in excellent yields with satisfactory ee values.