A practical and efficient Rh(III)-catalyzed aerobic C-H activation has been developed for the facile synthesis of a broad range of indoles from simple anilines and alkynes. The protocol could be conducted under mild conditions and used environmentally friendly oxygen as the sole clear oxidant.

A new strategy for selective insertion of metal carbenes into C-N bond has been developed via Pd-catalyzed C-N bond activation. A series of aminals and α-diazoesters with different substituents were successfully incorporated even in 0.1 mol % of catalyst under mild conditions, affording a wide range of α,β-diamino acid esters with quarternary carbon-centers. Preliminary mechanistic studies uncovered that the unique electrophilic cyclopalladated species could easily react with diazoacetates to generate a Pd-carbenoid intermediate which was involved in the catalytic cycle.

A first example of low-energy blue-lightmediated formal Doyle−Kirmse reaction for gem-difluoroallylation of aryl diazoesters has been developed. A variety of highly functionalized gem-difluoroallyl containing esters bearing transformable sulfur and bromine groups were efficiently assembled with broad substrate scope under mild, catalyst-free, and additive-free conditions. The reaction represents a practical and environmentally friendly approach for C−CF 2 bond formation based on rearrangement strategy, which will find potential applications among drug discovery and development.