Regioselective Oxyamination of Biaryls Using Nitroarenes

Biaryl frameworks are pivotal in natural products, pharmaceuticals, agrochemicals, and materials, with the 2'-amino-2'-hydroxy-1,1'-biaryl motif being especially valuable for catalysis and bioactivity. However, synthesizing these non-C₂-symmetric biaryls efficiently and regioselectively remains challenging due to limitations in current methods, such as prefunctionalization and structural constraints. Herein, we report a regioselective oxyamination of cyclometalated biaryl lanthanum reagents using nitroarenes. This lanthanum-based approach uniquely utilizes the oxophilicity and nucleophilicity of organolanthanum intermediates, enabling dual incorporation of oxygen and nitrogen into biaryl skeletons. A proposed 8-membered metallacycle intermediate avoids undesired nitrosoarene formation, delivering 2'-amino-2'-hydroxy-1,1'-biaryls with high efficiency. This one-pot, step-economical and transition-metal-free method achieves exceptional regioselectivity and a broad substrate scope, addressing longstanding challenges in biaryl functionalization and providing significant implications for catalysis, drug development, and materials science.