Generalized Chemoselective Transfer Hydrogenation/Hydrodeuteration

Abstract A generalized, simple and efficient transfer hydrogenation of unsaturated bonds has been developed using HBPin and various proton reagents as hydrogen sources. The substrates, including alkenes, alkynes, aromatic heterocycles, aldehydes, ketones, imines, azo, nitro, epoxy and nitrile compounds, are all applied to this catalytic system. Various groups, which cannot survive under the Pd/C/H 2 combination, are tolerated. The activity of the reactants was studied and the trends are as follows: styrene>diphenylmethanimine>benzaldehyde>azobenzene>nitrobenzene>quinoline>acetophenone>benzonitrile . Substrates bearing two or more different unsaturated bonds were also investigated and transfer hydrogenation occurred with excellent chemoselectivity. Nano‐palladium catalyst in situ generated from Pd(OAc) 2 and HBPin extremely improved the TH efficiency. Furthermore, chemoselective anti‐Markovnikov hydrodeuteration of terminal aromatic olefins was achieved using D 2 O and HBPin via in situ HD generation and discrimination. magnified image