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Stabilized AlHCl2·(THF)2 hydroaluminates RCCH with exceptional chemo-, regio- and stereoselectivity under efficient ZrCl2(η-C5Me5)2 catalysis (2–5 mol%). The resulting vinyl alanes undergo palladium cross-coupling with a wide range of sp2 electrophiles (aryl, heteroaryl and vinyl halides/pseudohalides) in good to excellent yields.