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

Yidong Wang; Peichao Zhang; Xiaoyu Di; Qiang Dai; Zhan-Ming Zhang; Junliang Zhang

doi:10.1002/anie.201709595

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

Angew Chem Int Ed Engl. 2017 Dec 11;56(50):15905-15909. doi: 10.1002/anie.201709595. Epub 2017 Nov 20.

Authors

Yidong Wang¹, Peichao Zhang¹, Xiaoyu Di¹, Qiang Dai¹, Zhan-Ming Zhang¹, Junliang Zhang^{1

2}

Affiliations

¹ Shanghai Key Laboratory of Green Chemistry and Chemical, Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N. Zhongshan Road, Shanghai, 200062, China.
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, China.

PMID: 29080246
DOI: 10.1002/anie.201709595

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/AuNTf₂ proved to be specifically efficient to promote the desymmetrization of N-allenamides in excellent yields with satisfactory ee values.

Keywords: allenamides; cyclization; enantioselectivity; gold; tetrahydrocarboline.

Publication types

Research Support, Non-U.S. Gov't