CO 2 -Promoted and Nickel-Catalyzed Direct Hydroallylation of Terminal Alkynes with Allylic Alcohols: Access to 1,4-Dienes.

CO 2 -promoted and Ni-catalyzed direct hydroallylation of terminal alkynes with allylic alcohols has been achieved. Various 1,4-dienes could be synthesized in good yield with excellent Markovnikov selectivity for alkyl- and aryl-substituted terminal alkynes under mild reaction conditions. A gram-scale reaction gives considerable yield. Preliminary mechanistic studies support the reaction pathway through sequential carboxylation/allylnickelation/lithium bicarbonate nickelation/transmetalation in the hydroallylation of alkynes with allylic alcohols in the presence of CO 2 .