title: Intramolecular Hydrogen Transfer Reactions Catalyzed by Pentamethylcyclopentadienyl Rhodium and Cobalt Olefin Complexes: Mechanistic Studies.
abstract: The mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp*M(VTMS)2] (1, M=Rh,2, M=Co, Cp* = C5Me5, VTMS = vinyltrimethylsilane) complexes has been studied using vinyl silane protected alcohols as substrates. Deuterium-labeled substrates have been synthesized and the regioselectivity of H/D transfers investigated using1H and2H NMR spectroscopy. The labeling studies establish a regioselective pathway consisting of alkene directed α C-H activation, 2,1 alkene insertion, and finally β-hydride elimination to give silyl enol ether products.
authors: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290.
authors: Andrew D
authors: AD
authors: Bolig
authors: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290.
authors: Thomas W
authors: TW
authors: Lyons
authors: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290.
authors: Darren T
authors: DT
authors: DiSalvo
authors: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290.
authors: Maurice
authors: M
authors: Brookhart