Rh(III)-Catalyzed, N-Amino-Directed C-H Coupling with α-Cyano-α-Diazoesters for 3-Aminocinnoline-4-Carboxylate Synthesis

The conventional synthetic practice is centered on the utility of reactant reactivity for the establishment of product inner core structure and frequently leads to the annihilation of product inner reactivity in the form of reactivity-depleting synthesis. This depletion of product inner reactivity can, essentially, block any further productive structural elaboration. Reactivity-propagating synthesis is proposed herein as a transformative synthetic practice, with both reactant reactivity and product inner reactivity programmed into the synthetic design and survival of product inner reactivity as the central goal. This exuberance of product inner reactivity can empower proliferated structural diversification into distinct chemical space. As a proof-of-concept demonstration, Rh(III)-catalyzed, N-amino-directed C-H coupling with α-cyano-α-diazoesters has been developed for 3-aminocinnoline-4-carboxylate synthesis. This synthetic methodology features the survival of product inner reactivity of two heteroatom N sites and amino and ester groups, allowing convenient versatile entry into varied open-chained and ring topology structures. The broad structural elaboration scope showcased herein promises reactivity-propagating synthesis as a powerful, broad-impact tool for synthetic development.