Cooperative Dinuclear Gold Catalysis Unlocking 1,2‐Reductive Elimination Elementary Reaction in Oxidative C─C Coupling

Abstract Cooperative catalysis enabled by dinuclear metal complexes can integrate the catalytic properties of each metal center, thus opening new avenues to achieve challenging reaction selectivity that are difficult to accomplish with mononuclear metal catalysts. Here, we present a cooperative catalysis strategy using a newly synthesized dinuclear PNP‐Au 2 catalyst, which positions two gold centers in close proximity, facilitating favorable geometric and electronic interactions for the synergistic activation of both coupling partners (alkynes and vinyl boron reagents) in the oxidative C─C coupling. It demonstrates a broad substrate tolerance for both terminal and internal alkynes, providing a versatile platform for the synthesis of enynes and dienes. Mechanistic and computational studies reveal a unique 1,2‐cooperative activation mode, significantly reducing the free energy barrier and stabilizing the key intermediates, thus promoting C─C bond formation in an efficient manner. The DFT calculations indicate a less explored 1,2‐reductive elimination elementary step. Interestingly, the use of B(O i Pr) 3 as an additive can effectively prevent the decomposition of dinuclear gold catalyst under oxidative fluoride‐containing conditions.