Ritter-type amination of C(sp3)-H bonds enabled by electrochemistry with SO42

• Published in: Nature communications Vol. 13; no. 1; p. 4138
• Main Authors: Zhang, Ling, Fu, Youtian, Shen, Yi, Liu, Chengyu, Sun, Maolin, Cheng, Ruihua, Zhu, Weiping, Qian, Xuhong, Ma, Yueyue, Ye, Jinxing
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 16.07.2022; Nature Publishing Group
• Subjects: 639/638/161; 639/638/403/933; Alkanes; Alkylbenzenes; Alzheimer's disease; Amination; Anions; Bonding; Carbon; Deuteration; Electrochemistry; Electrolysis; Humanities and Social Sciences; Hydrogen atoms; Laboratories; multidisciplinary; Nitrogen; Oxidation; Pharmaceuticals; Pharmacy; Protocol; Room temperature; Science; Science (multidisciplinary); Selectivity; Substrates; Sulfates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-31813-3

By merging electricity with sulfate, the Ritter-type amination of C(sp 3 )-H bonds is developed in an undivided cell under room temperature. This method features broad substrate generality (71 examples, up to 93% yields), high functional-group compatibility, facile scalability, excellent site-selectivity and mild conditions. Common alkanes and electron-deficient alkylbenzenes are viable substrates. It also provides a straightforward protocol for incorporating C-deuterated acetylamino group into C(sp 3 )-H sites. Application in the synthesis or modification of pharmaceuticals or their derivatives and gram-scale synthesis demonstrate the practicability of this method. Mechanistic experiments show that sulfate radical anion, formed by electrolysis of sulfate, served as hydrogen atom transfer agent to provide alkyl radical intermediate. This method paves a convenient and flexible pathway for realizing various synthetically useful transformations of C(sp 3 )-H bonds mediated by sulfate radical anion generated via electrochemistry. The amination of C(sp3)–H bonds is an appealing and challenging task in organic synthesis. Here, by using an electrogenerated sulfate radical an HAT agent, the authors report a practical Ritter-type amination of C(sp3)–H bonds.