Year: 2026
Type: article
Abstract: )─H arylation, providing direct access to challenging all-carbon quaternary stereogenic centers. Key to this success is the use of a specially designed BINOL-derived ligand, which enables efficient desymmetrization of gem-dimethyl groups through a rate- and enantio-determining C─H activation step. This catalytic system demonstrates remarkable functional group tolerance, affording a wide variety of arylated products in high yields (up to 85%) and with excellent enantioselectivities (up to 95:5 e.r.). Mechanistic studies, combining kinetic isotope effect measurements, deuterium labeling, and DFT calculations, reveal that the Ni-BINOL complex promotes a unique concerted metalation-deprotonation pathway assisted by ligand coordination and π-π interactions. This work establishes nickel as a powerful and sustainable alternative to precious metals for asymmetric C─H activation, opening new perspectives for the construction of enantioenriched quaternary carbon centers of high relevance in drug discovery and materials science.
Institution: University of Würzburg
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
Funder: European Commission
Award: G6496626793
OpenAlex ID: W7118436124