Metal‐Free Benzylic C−H Amination via Electrochemically Generated Benzylaminosulfonium Ions

• Published in: Chemistry : a European journal Vol. 23; no. 1; pp. 61 - 64
• Main Authors: Hayashi, Ryutaro, Shimizu, Akihiro, Song, Yetao, Ashikari, Yosuke, Nokami, Toshiki, Yoshida, Jun‐ichi
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.01.2017; Wiley Subscription Services, Inc
• Subjects: benzyl cations; Chemistry; Chemistry, Multidisciplinary; C−H amination; C−H functionalization; Derivatives; Electrochemical oxidation; electrochemistry; Electrode potentials; Iodides; Oxidation; Physical Sciences; Science & Technology; Synthesis; Toluene; Transformations; C-H amination; IODIDE REDUCTION; CATALYSIS; ELECTROLYTE; electrochemistry; oxidation; AMIDATION; BOND FORMATION; benzyl cations; DEPROTECTION; C-H functionalization; MILD; ETHERS; ESTERS; SULFILIMINES; C−H functionalization; C−H amination
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201604484

Electrochemical oxidation of toluene derivatives in the presence of N‐tosyldiphenylsulfilimine gave the corresponding benzylaminosulfonium ions, which were treated with tetrabutylammonium iodide under non‐electrolytic conditions to give N‐tosylbenzylamines. The transformation serves as a metal‐ and chemical‐oxidant‐free method for benzylic C−H amination. Because of high oxidation potential of N‐tosyldiphenylsulfilimine the present method can be applied to synthesis of various benzylamines from functionalized toluene derivatives. Electrochemical C−H amination: Electrochemical oxidation of toluene derivatives in the presence of N‐tosyldiphenylsulfilimine gave the corresponding benzylaminosulfonium ions, which were treated with tetrabutylammonium iodide under non‐electrolytic conditions to give N‐tosylbenzylamines. The transformation serves as a metal‐ and chemical‐oxidant‐free method for benzylic C−H amination.