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Updated: Sep 10, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Arylboration of Cyclic Enones via Cooperative Copper/Palladium Catalysis
Kian Mansour1, Piyas Saha1, Lukas Dellermann1
1Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
Abstract:
We report a Cu/Pd co-catalyzed method for the anti-selective arylboration of cyclic enones. A conjugate borylation/enolate trapping mechanism is proposed, facilitated by a high Pd:Cu ratio and use of JohnPhos as a ligand. Diastereoselectivity is sensitive to both aryl halide and enone, and no product epimerization is observed in situ, suggesting a stereodetermining transmetalation or reductive elimination event. Products are readily functionalized at the B(pin), ketone, and carbocyclic frameworks, providing access to complex carbocycles with high stereochemical control.
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