Axially Chiral 2-Hydroxybiaryls by Palladium-Catalyzed Enantioselective C–H Activation

This article describes the discovery and development of a palladium-catalyzed asymmetric C–H olefination of 2-hydroxybiaryls. The strategy allows a direct assembly of optically active, axially chiral 2-substituted-2′-hydroxybiaryls from readily available precursors and demonstrates that the native hydroxy unit of the substrates can work as an efficient directing group for the C–H activation. This represents a substantial advantage over other approaches that require the preinstallation of metal coordinating units. The simplicity of the approach and versatility of the products allow a practical and efficient synthesis of a broad variety of optically active binaphthyl derivatives.This work has received financial support from Spanish grants (Grants PID2019-108624RB-I00 and PID2019-110385GB-I00 funded by MCIN/AEI/10.13039/501100011033, Grant IHRC22-00009 funded by MCIN/ISCIII, and by the “European Union NextGenerationEU/PRTR” and ORFEO–CINQA network RED2018-102387-T), the Consellería de Cultura, Educación e Ordenación Universitaria (Grant ED431C 2021/25 and Grant ED431G 2019/03: Centro Singular de Investigación de Galicia accreditation 2019–2022) and the European Union (European Regional Development Fund-ERDF corresponding to the multiannual financial framework 2014–2020). We thank the Ministerio de Universidades for the FPU fellowship to L.G.S