Metal‐Free, Hindered, Regioselective Access to Multifunctional Groups Diarylamines via SNAr Substitution of P‐Nitroso Aromatic Methyl Ether by Arylamines

• Published in: Chemistry : a European journal Vol. 30; no. 11
• Main Authors: Zou, Shuliang, Zhang, Yazhou, Wu, Qin, Zhao, Tianming, Li, Yutao, Liu, Bing, Ma, Xianguo
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 21.02.2024; Wiley Subscription Services, Inc
• Subjects: amination; Amines; Charge transfer; Chemistry; Chemistry, Multidisciplinary; Functional groups; hindered; intermolecular nucleophilic aromatic substitution; nitroso arenes; Organic compounds; Physical Sciences; regioselective; Regioselectivity; Science & Technology; Substitution reactions; Substrates; ACTIVATION; nitroso arenes; ARYL ETHERS; ETHERIFICATION; BOND-CLEAVAGE; hindered; regioselective; KETONES; CROSS-COUPLINGS; intermolecular nucleophilic aromatic substitution; CHEMISTRY; amination; DERIVATIVES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202303421

Multifunctional groups diarylamines, an innovative product, efficiently produced from arylamines and p‐nitrosoanisole derivatives by intermolecular SNAr under weak acid conditions. This SNAr proceeds under mild reaction conditions, and more significantly, the substrates involved do not necessarily require strong electron‐withdrawing groups. Moreover, this SNAr is characterized by resistance to space crowding, tolerance to halogen and nitroso functional groups, and high regioselectivity. Mechanistic observations suggest that the SNAr is the result of the transfer of the positive charge center of the protonated nitroso group to the p‐methoxy group. Multifunctional groups diarylamines efficiently produced from arylamines and p‐nitrosoanisole derivatives by intermolecular SNAr under weak acid conditions. Relying on the catalysis of hydrogen protons, the SNAr reaction, which is endowed with resistance to space crowding, tolerance to halogen and nitroso groups, and high regioselectivity, can be carried out under mild conditions, even if the substrates involved do not have strong electron‐withdrawing groups.