Regioselective Oxyamination of Biaryls Using Nitroarenes DOI

Dandan Sun,

D. D. Fan,

Mingran Mao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

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

Language: Английский

Regioselective Oxyamination of Biaryls Using Nitroarenes DOI

Dandan Sun,

D. D. Fan,

Mingran Mao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

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

Language: Английский

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