Selective cross-coupling of ,-unsaturated nitriles with aldehydes or alcohols by hydrogen transfer catalysis towards -ketonitriles and glutaronitriles

beta-Ketonitriles and glutaronitriles are both valuable compounds in the chemical and pharmaceutical industries. We report here a novel ruthenium-catalyzed selective cross-coupling of alpha,beta-unsaturated nitriles with aldehydes or alcohols towards beta-ketonitriles and glutaronitriles via hydrogen transfer catalysis. Branch-selective hydroacylation of the feedstock chemical acrylonitrile and its derivatives produces versatile beta-ketonitriles using a wide range of non-chelating aldehydes or alcohols. Moreover, functionalized glutaronitriles have been obtained via cross-coupling of acrylonitrile and alcohols through a one-step tandem hydroacylation and Michael addition reaction. Mechanistic studies reveal that the reaction takes place via hydrogen transfer catalysis through a possible keteniminate ruthenium intermediate. A Ru-catalyzed selective hydroacylation of acrylonitriles with aldehydes or alcohols towards beta-ketonitriles is established. Glutaronitriles can be obtained through a one-step tandem hydroacylation and Michael addition of acrylonitrile and alcohols.