Abstract
AbstractAerobic oxidative coupling is a dehydrogenative organic transformation in which molecular oxygen acts as a re‐oxidant for the catalyst system. Pd has emerged as one of the most popular transition metal catalysts for such reactions. Combinations of Pd with other transition metal catalysts can also provide effective catalytic cycles together with highly atom‐ and step‐economical organic transformations. A synergic Pd catalyst system can promote such reactions with a high degree of efficiency based on a re‐oxidation step exhibiting improved kinetics in which two electrons are transferred from another transition metal. This occurs in conjunction with a lower energy barrier than that associated with direct re‐oxidation by molecular oxygen. This review highlights recent developments in aerobic oxidative coupling reactions catalyzed by synergic combinations of Pd with other transition metals. Highlighted reactions include dehydrogenative C−C bond formation such as arylation of arenes, heteroarenes, alkenes and dehydrogenative C−N and C−O bond formations with unsaturated hydrocarbons such as alkenes, 1,3‐dienes and allenes. Moreover, mechanistic insights into these aerobic reactions based on experimental, computational and optical studies are detailed.
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