Nickel-Catalyzed Reductive Alkyne Hydrocyanation Enabled by Malononitrile and a Formaldehyde Additive
Anthony F. Palermo, B Chiu, Purvish Patel, Sophie A. L. Rousseaux
Abstract
The development of a nickel-catalyzed reductive alkyne hydrocyanation is described using 2-methyl-2-phenylmalononitrile (MPMN), a C-bound electrophilic transnitrilation reagent. Reproducibility issues led to the detection of oxidized hemiaminal impurities within N, N -dimethylacetamide. These impurities release formaldehyde in situ, which was ultimately identified as a critical reaction additive. A range of diaryl and aryl-alkyl alkynes underwent hydrocyanation. Mechanistic experiments revealed that formaldehyde and MPMN undergo a Ni-catalyzed reductive coupling of two π-components, leading to the controlled release of glycolonitrile as the active cyanating agent.
Topics & Concepts
ChemistryHydrocyanationAlkyneReductive eliminationCatalysisMalononitrileOrganic chemistryNitrileNickelCyanationDimethylacetamideCombinatorial chemistrySolventCatalytic C–H Functionalization MethodsSulfur-Based Synthesis TechniquesSynthesis and Catalytic Reactions