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.