Abstract
Inter‐ and intramolecular palladium‐catalyzed allyl cross‐coupling reactions using allylindium generated in situ by treatment of allyl acetates with indium and indium trichloride in the presence of Pd^0^ catalyst and __n__BuNMe~2~ in DMF were successfully demonstrated. Allylindium species generated in situ by reductive transmetalation of π‐allylpalladium(II) complexes, obtained from a variety of allyl acetates in the presence of Pd^0^ catalyst together with indium and indium trichloride, were found to be capable of acting as effective nucleophilic coupling partners in Pd‐catalyzed cross‐coupling reactions. A variety of allyl acetates such as but‐1‐en‐3‐yl acetate, crotyl acetate, and 2‐methylallyl acetate afforded the corresponding allylic compounds in good yields in cross‐coupling reactions. Various electrophilic cross‐coupling partners such as aryl iodides and vinyl bromides and triflates participate in these reactions. Not only intermolecular but also intramolecular Pd‐catalyzed cross‐coupling reactions work equally well to produce the desired allylic coupling products in good yields.