Palladium‐Catalyzed Construction of Phthalides Bearing Two Adjacent Stereocenters through Retro‐oxa‐Michael Addition

• Published in: Chinese journal of chemistry Vol. 42; no. 23; pp. 3006 - 3012
• Main Authors: Liu, Li‐Xia, Niu, Tong, Bai, Yu‐Qing, Zhou, Yong‐Gui
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 01.12.2024; Wiley; Wiley Subscription Services, Inc
• Subjects: Alkylation; Asymmetric allylic alkylation; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Chemoselectivity; Dynamic kinetic resolution; Lactones; Optical activity; Palladium; Palladium catalysis; Physical Sciences; Retro‐oxa‐Michael addition; Science & Technology; Stereochemistry; Stereoselectivity; Asymmetric allylic alkylation; ASYMMETRIC TRANSFER HYDROGENATION; CARBONATES; Chemoselectivity; ALLYLATION; Dynamic kinetic resolution; Stereochemistry; ALKYLATIONS; TERTIARY; Retro-oxa-Michael addition; Lactones; KETONES; DIPHOSPHINE LIGANDS; Palladium catalysis; ALLYLIC SUBSTITUTION
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.202400612

Comprehensive Summary Optically active phthalides are prevalent in many natural and bioactive products. Herein, a novel dynamic kinetic resolution of isobenzofuranone derivatives through palladium‐catalyzed asymmetric allylic alkylation has been developed to synthesize phthalide derivatives bearing vicinal quaternary and tertiary stereocenters with high yields, showing excellent chemo‐, enantio‐ and diastereoselectivity. Furthermore, gram‐scale experiment underwent smoothly and the transformation of product could build a bridged bicyclic skeleton. A novel dynamic kinetic resolution of isobenzofuranone derivatives through palladium‐catalyzed asymmetric allylic alkylation has been developed to synthesize phthalide derivatives bearing vicinal quaternary and tertiary stereocenters with high yields, showing excellent chemo‐, enantio‐ and diastereoselectivity.