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Updated: Jul 11, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
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Nickel-Catalyzed Reductive Alkyne Hydrocyanation Enabled by Malononitrile and a Formaldehyde Additive
Anthony F Palermo1, Benjamin S Y Chiu1, Purvish Patel1
1Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
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.
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