Access to Aryl‐Naphthaquinone Atropisomers by Phosphine‐Catalyzed Atroposelective (4+2) Annulations of δ‐Acetoxy Allenoates with 2‐Hydroxyquinone Derivatives. Issue 43 (11th September 2019)

• Record Type: Journal Article
• Authors: Chen, Xin; Gao, Dingding; Wang, Dong; Xu, Tong; Liu, Wei; Tian, Ping; Tong, Xiaofeng
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 43(2019)
• Page Start: 15334
• Page End: 15338
• Publication Date: 2019-09-11
• Subjects: allenes -- annulations -- atropisomer -- organocatalysis -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201908923
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Although asymmetric phosphine catalysis is a powerful tool for the construction of various chiral carbon centers, its synthetic potential toward an enantioenriched atropisomer has not been explored yet. Reported herein is a phosphine‐catalyzed atroposelective (4+2) annulation of δ‐acetoxy allenoates and 2‐hydroxyquinone derivatives. The reaction provides expedient access to aryl‐naphthaquinone atropisomers by the de novo construction of a benzene ring. The two functionalities of the catalyst, a tertiary phosphine (Lewis base) and a tertiary amine (Brønsted base), cooperatively enable this process with high regio‐ and enantioselectivities. Abstract : Catalyst co‐op : A phosphine‐catalyzed atroposelective (4+2) annulation of δ‐acetoxy allenoates and 2‐hydroxyquinone derivatives provides expedient access to aryl‐naphthaquinone atropisomers by the de novo construction of a benzene ring. The two functionalities of the catalyst, a tertiary phosphine (Lewis base) and a tertiary amine (Brønsted base), cooperatively enable this process with high regio‐ and enantioselectivities.