Nickel-Catalyzed Hydrocyanation and Functionalization of Alkenes

Nickel-catalysed hydrocyanation of alkenes has emerged as a versatile and atom‐economical route to nitriles, which serve as key intermediates in pharmaceuticals, agrochemicals and polymer precursors. The catalytic cycle typically involves oxidative addition of hydrogen cyanide (HCN) to a nickel(0) centre, formation of nickel–hydride and nickel–cyanide species, migratory insertion of the alkene into the metal–hydride bond and reductive elimination to furnish the aliphatic nitrile while regenerating the active nickel(0) catalyst. Advances in ligand design—ranging from diphosphites and bidentate phosphines to chiral phosphine‐phosphite assemblies—have enabled remarkable improvements in activity, regiocontrol and enantioselectivity. Optimised operational protocols now achieve turnover frequencies exceeding 300 000 h–1 in model styrene hydrocyanations. Beyond simple addition, nickel catalysts can engage nitrile products in further C–C and C–heteroatom coupling, effect reversible C–CN bond cleavage or drive tandem sequences that furnish elaborated molecular scaffolds. Challenges remain in handling the inherent toxicity of HCN, suppressing catalyst deactivation and precisely controlling regio‐ and stereochemical outcomes, yet recent methodological breakthroughs point to broad applicability in sustainable fine‐chemical production and late‐stage derivatisation of complex frameworks.

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Nickel-Catalyzed Hydrocyanation and Functionalization of Alkenes publication trend

The graph below shows the total number of articles in nickel-catalyzed hydrocyanation and functionalization of alkenes across all publications each year (not limited to Nature Index journals).

Technical terms

Hydrocyanation: Addition of hydrogen cyanide (HCN) across a carbon–carbon double bond to yield a nitrile.

Nitrile: Organic functional group containing a carbon–nitrogen triple bond (C≡N).

Turnover frequency (TOF): Number of catalytic cycles performed by each active site per unit time.

Enantioselectivity: Preference of a chiral catalyst to form one enantiomer over its mirror image.

Ligand: Molecule coordinating to a metal centre to influence its reactivity and selectivity.

References

1. Nickel(BiPhePhos)-Catalyzed Hydrocyanation of Styrene—Highly Increased Catalytic Activity by Optimized Operational Procedures. Catalysts (2024).
2. Mechanistic Investigation on Hydrocyanation of Butadiene: A DFT Study. Catalysts (2020).
3. Enantioselective Nickel‐Catalyzed Hydrocyanation of Homostilbenes. European Journal of Organic Chemistry (2023).
4. Reversible C–CN Bond Cleavage by a Formal Dinickel(I) Hydride Cation. Organometallics (2024).