| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1335838 | Polyhedron | 2016 | 7 Pages |
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 using 1H and 2H 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.
Graphical abstractThe mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp∗M(VTMS)2] (M = Rh, Co, Cp∗ = C5Me5) complexes has been studied using vinyl silane protected alcohols as substrates. Using deuterium-labeled substrates, the regioselectivity of H/D transfers was investigated using NMR spectroscopy. These studies establish a regioselective pathway involving alkene directed α-C–H activation, 2,1 alkene insertion, and finally β-hydride elimination to give silyl enol ether products.Figure optionsDownload full-size imageDownload as PowerPoint slide
