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 Cl₂Pd(DPEphos), DIBAL-H, and TFP (catalyst A) with InCl₃ as a cocatalyst.