Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement.
A combination of physical organic experiments and quantum chemical calculations were used to construct a detailed mechanistic model for the Ni(0)-N-heterocyclic carbene-catalyzed vinylcyclopropane-cyclopentene rearrangement that involves a mutistep oxidative addition/haptotropic shift/reductive elimination pathway. No evidence for the intermediacy of radicals or zwitterions was found. The roles of substituents on the vinylcyclopropane substrate and variations in the ligands on Ni were evaluated. It is postulated that bulky carbene ligands facilitate formation of the active catalyst species.
Wang
Selina C
SC
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
Troast
Dawn M
DM
Conda-Sheridan
Martin
M
Zuo
Gang
G
LaGarde
Donna
D
Louie
Janis
J
Tantillo
Dean J
DJ
D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry*; D003521:Cyclopropanes / Q000737:chemistry*; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
D003517:Cyclopentanes; D003521:Cyclopropanes; D014753:Vinyl Compounds; D009532:Nickel