Use of InCl3 as a Cocatalyst and a Cl2Pd(DPEphos)−P(2-Furyl)3 Catalyst System for One-Pot Hydrometalation−Cross-Coupling and Carbometalation−Cross-Coupling Tandem Processes

One-pot conversion of alkynes to regio- and stereodefined alkenylmetals containing Al and Zr via hydrometalation or carbometalation followed by their Pd-catalyzed cross-coupling with (E)-ICH=CHBr or (E)-ICH=CHCl proceeds cleanly and selectively to give the corresponding 1-halo-1,3-dienes in excellent yields using a catalyst system consisting of Cl(2)Pd(DPEphos), DIBAL-H, and TFP (catalyst A) with InCl(3) as a cocatalyst.