Nickel-Catalyzed Reductive Allylation of Aldehydes with Allylic Alcohols in the Presence of CO 2 .

CO 2 -assisted and Ni-catalyzed direct reductive allylation of aldehydes utilizing allylic alcohols as allylic precursor has been reported. Various homoallyl alcohols could be synthesized in excellent yield with enhanced regioselectivity and stereoselectivity for alkyl- and aryl-substituted aldehydes under mild conditions. For different substrates, proper collocation of the catalytic precursor and ligand is crucial. Preliminary mechanistic studies supported the reaction pathway through a sequential allyl hydrocarbonate formation/allylnickelation/coordination insertion process by the Ni(I)/Ni(III) catalytic cycle, which has been proven by cyclic voltammetry analysis.