ja8b02834_si_001.pdf (3.15 MB)
Decarboxylative Hydroalkylation of Alkynes
journal contribution
posted on 2018-04-17, 00:00 authored by Nicholas
A. Till, Russell T. Smith, David W. C. MacMillanThe 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 CO2 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.