Intramolecular hydrogen transfer reactions catalyzed by pentamethylcyclopentadienyl rhodium and cobalt olefin complexes: Mechanistic studies

The mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp * M(VTMS) 2 ] ( 1 , M=Rh, 2 , M=Co, Cp* = C 5 Me 5 , 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 using 1 H and 2 H 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

Intramolecular hydrogen transfer reactions catalyzed by pentamethylcyclopentadienyl rhodium and cobalt olefin complexes: Mechanistic studies

The mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp(*)M(VTMS)(2)] (1, M=Rh, 2, M=Co, Cp* = C(5)Me(5), 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 using (1)H and (2)H 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