A highly efficient head‐to‐tail dimerization of a styrene was developed using a cationic palladium(II)‐catalyzed selective CC bond forming reaction. The complex [AllylPd(PPh3)]+OTf−, which is believed to generate ‘palladium hydride’ (PdH), catalyzed the dimerization of various styrenes in excellent yields as single isomers. This Pd(II)‐catalyzed reaction provides a new economical CC bond forming method.
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