Benzimidates as -Diamidation and Amidoindolyzation Cascade Synthons with a Hydrated Ni Catalyst.

We contributed a new benzimidate chemistry through moisture-insensitive Ni/Ni-Fe combo-catalysis for a simultaneous 2-3 bond-forming -diamidation and amidoindolyzation cascade reaction to construct symmetrical and unsymmetrical -(arylmethylene)amides and indolo(arylmethylene)amides, using emerging benzimidate synthons. The operational simplicity, mild nature, generality, and robustness of the strategy were validated through syntheses of a wide range of new molecules, labile sugar-based chiral compounds, and pharmaceuticals with high yields under the same reaction conditions.