DOI: 10.1021/acs.orglett.6c02869 ISSN: 1523-7060
Electrochemical One- or Two-Electron Oxidation Enables Chemoselective α-Amino C(sp3)–H Arylation and Cyanation
Shengtao Zhang, Mohan Bu, Zainure Osman, Ziren Chen, Fei Xue, Bin Wang, Yu Xia, Yonghong Zhang, Shicheng Dong, Shaofeng Wu, Chenjiang LiuAbstract
A controllable one- vs two-electron electrochemical strategy enables chemoselective α-amino C(sp3)–H arylation (secondary amines) or α-cyanation (tertiary N-aryl-THIQs) using 1,4-dicyanobenzene as a dual-function aryl/cyano source. Simple adjustments of electrolysis parameters divert tertiary amines to two-electron iminium/CN– trapping and secondary amines to one-electron radical/radical-anion cross-coupling. The operationally simple, oxidant-free protocol delivers up to 98% yield, tolerates diverse (hetero)arenes, and is demonstrated on a 2 mmol continuous-flow scale.