Ruthenium-Catalyzed alpha-Olefination of Nitriles Using Secondary Alcohols

Ruthenium(II) pincer-catalyzed alpha-olefination of nitriles is reported. This simple protocol provides a transformation for the catalytic synthesis of beta-disubstituted vinyl nitrites using secondary alcohols. This catalytic method has an extensive substrate scope, as arylmethyl nitrites, heteroaryl-methyl nitrites, and aliphatic nitriles as well as cyclic, acyclic, symmetrical, and unsymmetrical secondary alcohols are all employed in the reaction to provide diverse alpha-vinyl nitriles. C=C bond formation proceeds through activation of the O-H bond of secondary alcohols via an unsaturated 16-electron intermediate ruthenium pincer complex and further condensation of in situ-formed ketones with nitriles. Remarkably, H-2 and H2O are the only byproducts of this method.