Modular construction of functionalized anilines via switchable C-H and N-alkylations of traceless N-nitroso anilines with olefins

A switchable C-H alkylation and N-alkylation with great chemo- and site-selectivity enabled by N-nitroso anilines was developed, affording functionalized anilines, hydrazines and heterocycles. The exploration of strain-release as the key driving force with structurally diverse olefins enabled mild and practical sequential C-H and C-C or C-O cleavage. Notably, N-nitroso anilines could act as traceless directing groups to enable indole synthesis via dehydrogenative coupling with styrenes.

Automated summary

A switchable C-H alkylation and N-alkylation method with high chemo- and site-selectivity was developed using N-nitroso anilines, which yielded functionalized anilines, hydrazines, and heterocycles. The study explored strain-release as the driving force for mild and practical sequential C-H and C-C or C-O cleavage reactions with structurally diverse olefins. Interestingly, N-nitroso anilines were found to act as traceless directing groups for indole synthesis via dehydrogenative coupling with styrenes.