An aniline dication-like transition state in the Bamberger rearrangement

• Published in: Beilstein journal of organic chemistry Vol. 9; no. 1; pp. 1073 - 1082
• Main Authors: Yamabe, Shinichi, Zeng, Guixiang, Guan, Wei, Sakaki, Shigeyoshi
• Format: Journal Article
• Language: English
• Published: Germany Beilstein-Institut 03.06.2013
• Subjects: Bamberger rearrangement; Chemistry; DFT calculations; Full Research Paper; N-phenylhydroxylamine; proton transfer; reactive intermediates; transition states; proton transfer; transition states; Bamberger rearrangement; reactive intermediates; N-phenylhydroxylamine; DFT calculations

A Bamberger rearrangement of N -phenylhydroxylamine, Ph–N(OH)H, to p -aminophenol was investigated by DFT calculations for the first time. The nitrenium ion, C 6 H 5 –NH + , suggested and seemingly established as an intermediate was calculated to be absent owing to the high nucleophilicity of the wa...