Catalytic Asymmetric Reductive Acyl Cross-Coupling: Synthesis of Enantioenriched Acyclic α,α-Disubstituted Ketones

2013/05/02 by Alan H. Cherney, Nathaniel T. Kadunce, Sarah E. Reisman · 3 citations
Chemistry · #Asymmetric Hydrogenation and Catalysis #Catalytic C–H Functionalization Methods #Radical Photochemical Reactions

paper · doi:10.1021/ja402922w

openalex publication_date 2013/05/02 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

The first enantioselective Ni-catalyzed reductive acyl cross-coupling has been developed. Treatment of acid chlorides and racemic secondary benzyl chlorides with a Ni(II)/bis(oxazoline) catalyst in the presence of Mn(0) as a stoichiometric reductant generates acyclic α,α-disubstituted ketones in good yields and high enantioselectivity without requiring stoichiometric chiral auxiliaries or pregeneration of organometallic reagents. The mild, base-free reaction conditions are tolerant of a variety of functional groups on both coupling partners.

Citations

• A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium
• Palladium-Catalyzed Asymmetric Allylic α-Alkylation of Acyclic Ketones

Cited by

• Mechanisms of Nickel-Catalyzed Cross-Coupling Reactions
• Intra‐ and Intermolecular Nickel‐Catalyzed Reductive Cross‐Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides
• Sarah E. Reisman [wikipedia]

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