How to make C–N bonds using boronic acids without transition metals

What is it about?

This tutorial review discusses recent advancements in boronic acid-mediated C-N bond-forming reactions (amination, amidation, nitration, and nitrosation) without the need for transition-metals. Emphasizing the less-explored aspect of boronic acids as nucleophiles, it covers reagents and mechanisms. The paper underscores their sustainable role in synthesizing amines, amides, nitroso, and nitro compounds, contributing to eco-friendly approaches in pharmaceuticals, polymers, and materials synthesis.

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Photo by Jakayla Toney on Unsplash

Photo by Jakayla Toney on Unsplash

Why is it important?

- Tutorial review on recent advances in sustainable C-N bond-formation. - Focus on less-explored aspects of boronic acids as carbon-nucleophiles. - Emphasis on transition-metal-free utilization, away from their traditional role in transition-metal-catalyzed reactions (Suzuki, Hayashi-Miyaura, etc.). - Discussion of reagents and mechanisms - Contribution to environmentally friendly synthesis in pharmaceuticals, polymers, and materials. Key learning points (1) Formation of tetrahedral boronates induces a nucleophilic activation of the carbon backbone of boronic acids and their derivatives (boronic acids, boronate esters, or potassium organotrifluoroborates). (2) N–B coordination of a variety of N-LG reagents (LG = Leaving Group) followed by 1,2-C(B–N)-shift triggers C–N bond formation in the absence of transitionmetals. (3) Deoxygenation of nitro and nitroso groups turns them into useful nitrogen electrophiles for amine formation. (4) Acylboron compounds react with N-LG reagents (LG = leaving group) through their carbonyl group to form hemiaminals that evolve to amides.

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