Unlocking Migratory Insertion in Gold Redox Catalysis

Exploration of elementary reactions in organometallic catalysis is an important method with which to discover new reactions. In this article, we report a gold(I)-catalyzed iodo-alkynylation of benzyne involving the merging of challenging migratory insertion and an oxidative addition process in gold catalytic cycle. A wide range of structurally diverse alkynyl iodides are good coupling partners in this iodo-alkynylation transformation. Both aliphatic and aromatic alkynyl iodides can react with benzynes smoothly to afford highly functionalized 1,2-disubstituted aromatics in moderate to good yields. Its good functional group compatibility and late-stage application of complex molecules demonstrate its synthetic robustness. Studies of the mechanism reveals the feasibility of oxidative addition and the DFT calculations demonstrate the possible migratory insertion of benzyne into Au-III-carbon bonds in the Au-I/Au-III redox catalytic cycle, representing an important step towards an elementary reaction in gold chemistry research.

Automated summary

In this study, a gold(I)-catalyzed iodo-alkynylation of benzyne was reported, which involves the merging of migratory insertion and oxidative addition processes in the gold catalytic cycle. Various alkynyl iodides, both aliphatic and aromatic, are good coupling partners in this transformation, leading to highly functionalized 1,2-disubstituted aromatics in moderate to good yields. The reaction exhibits good compatibility with functional groups and can be applied to complex molecules, demonstrating its synthetic robustness. Mechanistic studies suggest the feasibility of oxidative addition and DFT calculations support the possible migratory insertion of benzyne into Au-III-carbon bonds, representing an important step towards understanding elementary reactions in gold chemistry research.