Pd‐Catalyzed MIA‐Directed Acetoxylation of Benzylamines and Computational Study

• Published in: European journal of organic chemistry Vol. 2022; no. 37
• Main Authors: Meng, Yue‐Ning, Zhao, Shi‐Chen, Liu, Peng‐Yu, Hu, Dianwen, Wang, Shuai, He, Yu‐Peng, Yu, Fang
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 07.10.2022; Wiley Subscription Services, Inc
• Subjects: Acetoxylation; Benzylamines; Chemistry; Chemistry, Organic; C−H functionalization; Methoxyiminoacyl; Palladium; Pd-catalyzed; Phenylalanine; Physical Sciences; Science & Technology; Substrates; MECHANISM; Acetoxylation; Pd-catalyzed; ARYLATION; BONDS; Benzylamines; C(SP)-H; C-H functionalization; Methoxyiminoacyl
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202200728

The direct acetoxylation of substituted benzylamines has been accomplished through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. A diverse array of phenylalanine substrates is amenable to this protocol, providing acetoxylation benzylamine derivatives with good to high efficiency. Computational results revealed that HOAc enhanced the stability of Pd−O bond, which obviously accelerate the reductive elimination step of the acetoxylation process. A highly efficient MIA‐mediated acetoxylation of substituted benzylamines was reported, which tolerate various substituent groups with good to high yields. DFT‐Studies showed that a weaker electrostatic attraction of HOAc to OAc led to the preferential formation of a five‐membered cyclopalladium intermediate (OAc−Pd−C).