Nitrate Reduction for Deaminative Suzuki-Miyaura Coupling of Anilines

Abstract

We present a deaminative Suzuki-Miyaura-type coupling (SMC) of anilines with nitrate as a diazotization reagent, which integrates transition-metal catalysis with nitrate-based diazonium chemistry for the first time. The synergistic reduction of nitrate by bisulfite and boronic acids allows for both oxidative diazotization with low-valent transition metal redox transformations simultaneously. The reaction utilizes low-hazard, readily available starting materials and reagents. In comparison to previous diazonium-based Suzuki-Miyaura-couplings, the in-situ oxidation of anilines by reduction of nitrate allows larger functional group tolerance.