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

We contributed a new benzimidate chemistry through moisture-insensitive NiII/NiII-FeIII combo-catalysis for a simultaneous 2-3 bond-forming gem-diamidation and amidoindolyzation cascade reaction to construct symmetrical and unsymmetrical gem-(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.