A general bismuth-based platform for the catalytic construction of carbon–nitrogen bonds and beyond.

The amino moiety is a fundamental functional group with essential functions across the chemical and life sciences, including agrochemical and pharmaceutical research and manufacture, polymer chemistry, and biochemistry. Therefore, there is a well-acknowledged need for new and more sustainable methods to construct C-N bonds. Most procedures for C-N bond formation rely on the use of toxic and expensive transition metal catalysts, which are notoriously impeded by undesired -hydride elimination and/or poor site selectivity. Consequently, the search for new and more sustainable catalytic paradigms in synthesis has shifted towards the main group elements. Bismuth was recently demonstrated to moonlight both as a noble or first row transition metal, displaying reactivity in 1-electron and 2-electron processes at will. This dichotomy in reactivity of low-valent Bi complexes could potentially be crucial in addressing the long-standing issues encountered in CN bond formation. Thus, ClaN-Bi aims to discover and develop new catalytic CN cross-coupling reactions to generate both aliphatic and aromatic amines by exploiting the new Bi(I)/(II)/(III) redox platform.