Elementary Steps in Olefin Metathesis: Nickelacyclobutanes via Cycloaddition to Nickel Carbenes.

ABSTRACT: Olefin metathesis and cyclopropanation, major reactions in the synthetic toolbox, are predominantly catalyzed by platinum-group metals. First-row transition metal alternatives are desirable from the perspective of supply-chain sustainability. Although cyclopropanation by nickel catalysts is well established, limited evidence exists for the chemical feasibility of the cycloaddition step essential for inner-sphere cyclopropanation or olefin metathesis. We describe Ni(PP)(=CPh₂) complexes that provide this missing evidence. These complexes react with styrene and phenyl vinyl sulfone (PVS) to form β-H elimination products that imply nickelacyclobutane (NiCB) intermediates. For the PVS system, the NiCB could be observed directly by NMR analysis and X-ray crystallography. This is the

SUBMITTER: Cormier SK 

PROVIDER: S-EPMC12272553 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature