Work

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

Year: 2026

Type: article

Abstract: 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.

Source: Angewandte Chemie

DOI: 10.1002/ange.8854855

Authors: Hyeontaek Nam, Seji Jang, Dongwook Kim, Sangwon Seo

Institutions: Daegu Gyeongbuk Institute of Science and Technology, Institute for Basic Science

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,790

Funders: National Research Foundation of Korea, Daegu Gyeongbuk Institute of Science and Technology