Decarboxylative Hydroalkylation of Alkynes Article Swipe

View

Related Concepts

Chemistry Alkyl Intermolecular force Radical Nucleophile Combinatorial chemistry Alkyne Hydrogen atom Nickel Hydrogen bond Migratory insertion Medicinal chemistry Stereochemistry Organic chemistry Catalysis Molecule

Nicholas A. Till , Russell T. Smith , David W. C. MacMillan ·

YOU? · · 2018 · Open Access · · DOI: https://doi.org/10.1021/jacs.8b02834 · OA: W2799422945

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.