NiH‐Catalyzed Enantioconvergent α ‐Alkenylation of Carbonyl Compounds via Markovnikov Alkyne Hydronickellation

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Authors: HyeonTaek Nam, Seji Jang, Dongwook Kim, Sangwon Seo
Cited by: 2
References: 94

Abstract

β-Methylene carbonyl motifs constitute privileged structural frameworks that play vital roles as a pharmacophore and serve as key intermediates in the assembly of architecturally complex molecules. Despite their synthetic importance, asymmetric approaches for their preparation remain scarce and are largely confined to substrate-controlled or stoichiometric chiral auxiliary methods. Herein, we report a nickel hydride-catalyzed enantioconvergent α-alkenylation of carbonyl compounds with alkynes, providing a direct and general route to α-chiral β-methylene carbonyl derivatives. The transformation proceeds via Markovnikov-selective alkyne hydronickellation followed by nickel-radical recombination to forge the α-stereogenic center, delivering the desired products with high levels of regio- and enantioselectivity. The protocol accommodates a wide range of alkynes and α-halocarbonyl partners, displays excellent functional group tolerance, and can be applied to the modification of biologically relevant molecules. Mechanistic investigations indicate that a partially protic Ni(II)H species governs the observed regioselectivity, while enantio-discrimination occurs during the radical capture step. This work establishes NiH catalysis as a versatile platform for expanding the synthetic repertoire for enantioenriched β-methylene carbonyl architectures.

Fields of Study & Subjects

Catalytic C–H Functionalization Methods Radical Photochemical Reactions Catalytic Cross-Coupling Reactions

Publication details

Journal / source
Angewandte Chemie International Edition
Publisher
Wiley
Volume
65
Issue
17
Pages
e8854855–e8854855
Publication date
15 March 2026
Language
EN