Nickel‐Catalyzed Cyanoalkylation of Ketone Derivatives

Cyanoalkylation de dérivés de cétones catalysée par le nickel

Anaïs Coffinet (1) , Vincent Levacher (1) , Isabelle Gillaizeau (2) , Jean-François Brière (1) , Sylvain Oudeyer (1)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 ICOA - Institut de Chimie Organique et Analytique

Although the metal-based catalyzed cyanomethylation of aldehydes is well-developed, a similar approach to ketones with acetonitrile derivatives remains a challenge. Thanks to Tolman type complexes, NiIIcomplexes with a pyridine(dicarboxamide) pincer ligand, an alternative metal-catalyzed (1-5 mol% catalyst) cyanomethylation of an array of isatins and activated ketones is reported at room temperature. High isolated yields (up to 99%) were obtained not only with the poorly acidic acetonitrile but also with more challenging substituted alkyl cyanide nucleophiles. The in situ generated putative ion paired catalysts [NiCR2CN]-Cat+ likely benefit from the cation part (Cs+ or n-Bu4N+) to facilitate their formation and catalytic activity

Mots clés: Cyanoalkylation; Organometallic catalysis; Nickel complexes; Ketone; Pincer ligand

Domaines: Chimie organique; Catalyse

Anaïs Coffinet, Vincent Levacher, Isabelle Gillaizeau, Jean-François Brière, Sylvain Oudeyer. Nickel‐Catalyzed Cyanoalkylation of Ketone Derivatives. Advanced Synthesis and Catalysis, 2023, Advanced Synthesis & Catalysis, 365, pp.156-160. ⟨10.1002/adsc.202201147⟩. ⟨hal-03922108⟩