Copper‐Assisted Amination of Boronic Acids for Synthesis of Bulky Diarylamines: Experimental and DFT Study

• Published in: Chemistry : a European journal Vol. 23; no. 51; pp. 12575 - 12584
• Main Authors: Levitskiy, Oleg A., Grishin, Yuri K., Sentyurin, Vyacheslav V., Magdesieva, Tatiana V.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 12.09.2017; Wiley Subscription Services, Inc
• Subjects: Acids; Activation energy; Amination; Aromatic compounds; Chemistry; Chemistry, Multidisciplinary; Copper; Copper compounds; density functional calculations; Nitroso compounds; Physical Sciences; reaction mechanisms; Science & Technology; steric hindrance; Synthesis; density functional calculations; steric hindrance; COUPLING REACTIONS; PD-CATALYZED AMINATION; ARYLATION; reaction mechanisms; copper; amination; ARYLBORONIC ACIDS
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.201702270

Comparative investigation of copper‐assisted oxidative and reductive amination showed that the latter was preferable for the synthesis of bulky diarylamines. DFT estimation of the mechanism of copper(I)‐assisted reductive amination of boronic acids with aryl nitroso compounds was performed and possible active species were identified. DFT estimation of the steric penalty revealed that the barrier for the transmetalation step for the hindered nitroso compound was almost the same as that for the unsubstituted one, whereas a bulky group in the boronic acid increased the activation energy. A DFT study of the influence of the electronic properties of the substituents in both reactants on the activation energy revealed that the optimal combination for the synthesis of unsymmetrical diarylamines to provide better yields was an electron‐rich aryl boronic acid and an electron‐deficient nitroso compound. By using these helpful guidelines, a series of new bulky diarylamines were obtained and fully characterized. Penalty prevention: Guidelines for choosing the optimal synthetic procedure leading to bulky unsymmetrical diarylamines were established based on experimental and computational data. DFT calculations of the mechanism of copper(I)‐assisted reductive amination of boronic acids with aryl nitroso compounds was performed and the steric penalty due to bulky groups in the reactants was estimated (see scheme).