Axially Chiral Dibenzazepinones by a Palladium(0)‐Catalyzed Atropo‐enantioselective C−H Arylation. (23rd July 2018)

• Record Type: Journal Article
• Authors: Newton, Christopher G.; Braconi, Elena; Kuziola, Jennifer; Wodrich, Matthew D.; Cramer, Nicolai
• Is Part Of: Angewandte Chemie. Volume 130:Number 34(2018)
• Page Start: 11206
• Page End: 11210
• Publication Date: 2018-07-23
• Subjects: Asymmetrische Katalyse -- Atropisomere -- Axialchiralität -- C-H-Aktivierung -- Palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201806527
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Atropo‐enantioselective C−H functionalization reactions are largely limited to the dynamic kinetic resolution of biaryl substrates through the introduction of steric bulk proximal to the axis of chirality. Reported herein is a highly atropo‐enantioselective palladium(0)‐catalyzed methodology that forges the axis of chirality during the C−H functionalization process, enabling the synthesis of axially chiral dibenzazepinones. Computational investigations support experimentally determined racemization barriers, while also indicating C−H functionalization proceeds by an enantio‐determining CMD to yield configurationally stable eight‐membered palladacycles.