Cu-Catalyzed Cross-Coupling of Nitroarenes with Aryl Boronic Acids to Construct Diarylamines

The development and study of a simple copper-catalyzed reaction of nitroarenes with aryl boronic acids to form diarylamines that uses phenyl silane as the stoichiometric terminal reductant is described. This cross-coupling reaction requires as little as 2 mol % of CuX and 4 mol % of diphosphine for success and tolerates a broad range of functional groups on either the nitroarene or the aryl boronic acid to afford the amine in good yield. Mechanistic investigations established that the cross-coupling reaction proceeds via a nitrosoarene intermediate and that copper is required to catalyze both the deoxygenation of the nitroarene to afford the nitrosoarene and C-NAr bond formation of the nitrosoarene with the aryl boronic acid.

Automated summary

A simple copper-catalyzed reaction involving nitroarenes and aryl boronic acids to form diarylamines has been described, with phenyl silane as the stoichiometric terminal reductant. The cross-coupling reaction requires low concentrations of CuX and diphosphine, tolerates a wide range of functional groups, and proceeds via a nitrosoarene intermediate catalyzed by copper.