Enantioselective Dearomative Cyclization Enabled by Asymmetric Cooperative Gold Catalysis. (4th August 2022)

• Record Type: Journal Article
• Authors: Zhao, Ke; Kohnke, Philip; Yang, Ziguang; Cheng, Xinpeng; You, Shu‐Li; Zhang, Liming
• Is Part Of: Angewandte Chemie. Volume 134:Number 37(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-04
• Subjects: Cyclization -- Dearomatization -- Enantioselectivity -- Gold Catalysis -- Metal-Ligand Cooperation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202207518
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A gold(I)‐catalyzed enantioselective dearomatization is achieved via metal‐chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1‐naphthols, 2‐naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes. Abstract : Gold‐ligand cooperation permits catalytic enantioselective dearomatization of 1‐naphthols, 2‐naphthols, and phenols. This work is facilitated by the development of a divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphine ligands. Enantiomeric excesses up to 98 % are realized. DFT calculations lend support to the cooperative nature of the catalysis and the observed stereochemical outcome.