Ni-Catalyzed Regioselective Hydrodimerization of Enamides with Unactivated Alkenes

Abstract

In this study, we described the Ni-catalyzed cross-hydrodimerization of enamides with unactivated alkenes under SiH/DTBP-mediated thermoredox conditions that was promoted by catalytic CuBr. The reaction afforded α-branched primary amines/secondary amides in good yields and with high regioselectivity through the formation of a C(sp³)–C(sp³) bond at the N-α-carbons. Excellent functional compatibility was observed across a wide range of sterically congested enamides and alkenes, including allylic branched enamides and 1,1-disubstituted alkenes. The use of chiral BiOx ligand enabled the formation of chiral amides with a high level of enantioselectivity. The present study offers a new entry for expediting the preparation of secondary amides appended to internal alkyl chains, complementing existing methods in the rapidly growing field of C(sp³)–C(sp³) bond construction via the hydrodimerization of two distinct alkenes.

Keywords

Enamide - Alkene - Nickel - Hydrodimerization - C(sp³)-C(sp³) bond

Publikationsverlauf

Eingereicht: 15. Mai 2025

Angenommen nach Revision: 19. Juni 2025

Accepted Manuscript online:
20. Juni 2025

Artikel online veröffentlicht:
04. August 2025

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