Journal of the American Chemical Society · 2018 · 185 citations · 19 references
Natural SciencesChemical EngineeringChemistryCatalysisOrganic ChemistryOrganometallic ChemistryCarboxylic AcidsHeterocycle SynthesisMigratory InsertionOrganic SynthesisOrganometallic SynthesisRadical ReactionsAlkene Migratory InsertionAlkyl Migratory InsertionAlkylation ReactionsAlkyne Migratory InsertionDecarboxylative CouplingHydrogen Atom TransferMigratory Insertion Into AlkynesMigratory Insertion Mechanism
The merger of open- and closed-shell elementary organometallic steps has enabled the selective intermolecular addition of nucleophilic radicals to unactivated alkynes. A range of carboxylic acids can be subjected to a CO 2 extrusion, nickel capture, migratory insertion sequence with terminal and internal alkynes to generate stereodefined functionalized olefins. This platform has been further extended, via hydrogen atom transfer, to the direct vinylation of unactivated C–H bonds. Preliminary studies indicate that a Ni-alkyl migratory insertion is operative.
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