Evidence for formation and different evolution of tertiary rhodium alkyl intermediates under rhodium-catalyzed deuterio-(hydro)formylation of 1-(n-pyridyl)-1-phenylethenes

Rhodium catalyzed deuterio(hydro)formylation of the isomeric vinylidenic substrates 1-(n-pyridyl)-1-phenylethenes with Rh/PPh3 catalyst, at 80 °C and 100 atm, occurs via an almost exclusive formation of the tertiary alkyl rhodium intermediate which can β-eliminate, undergo migratory insertion or oxidative addition of deuterium in a different degree depending on the position of nitrogen atom.