Synthesis of Allenes by Hydroalkylation of 1,3-Enynes with Ketones Enabled by Cooperative Catalysis

A method for the synthesis of allenes by the addition of ketones to 1,3-enynes by cooperative Pd(0)Senphos/B(C6F5)3/NR3 catalysis is described. A wide range of aryl- and aliphatic ketones undergo addition to various 1,3-enynes in high yields at room temperature. Mechanistic investigations revealed a rate-determining outer-sphere proton transfer mechanism, which was corroborated by DFT calculations.