Synlett
DOI: 10.1055/a-1299-3009
letter

Electrochemical Oxidative C–H Thiocyanation or Selenocyanation of Imidazopyridines and Arenes

Ting Cui
a  College of Chemistry and Materials Science, Nanjing Normal University; Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control; Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, P. R. of China
,
Xiaofeng Zhang
a  College of Chemistry and Materials Science, Nanjing Normal University; Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control; Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, P. R. of China
,
Jun Lin
a  College of Chemistry and Materials Science, Nanjing Normal University; Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control; Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, P. R. of China
b  Changzhou Innovation and Development Institute, Nanjing Normal University, Changzhou 213022, P. R. of China
,
Zitong Zhu
a  College of Chemistry and Materials Science, Nanjing Normal University; Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control; Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, P. R. of China
,
Ping Liu
a  College of Chemistry and Materials Science, Nanjing Normal University; Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control; Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, P. R. of China
b  Changzhou Innovation and Development Institute, Nanjing Normal University, Changzhou 213022, P. R. of China
,
Peipei Sun
a  College of Chemistry and Materials Science, Nanjing Normal University; Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control; Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Nanjing 210023, P. R. of China
› Author Affiliations
This work was supported by the National Natural Science Foundation of China (Project 21672104, 21502097) and the Priority Academic Program Development of Jiangsu Higher Education Institutions.


Abstract

Regioselective electrochemical oxidative C–H thiocyanation or selenocyanation of imidazopyridines was achieved by using an undivided electrolytic cell. Transition-metal- and oxidant-free conditions are striking features of this protocol. A library of thiocyanated imidazopyridines with a broad range of functional groups were synthesized in high yields. This method was also applicable to the thiocyanation or selenocyanation of some electron-rich arenes.

Supporting Information



Publication History

Received: 12 September 2020

Accepted after revision: 28 October 2020

Publication Date:
28 October 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
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  • 27 2-Phenylimidazo[1,2-a]pyridin-3-yl Thiocyanate (3a):21a Typical Procedure An undivided 25 mL three-necked flask was charged with 2-phenylimidazo[1,2-a]pyridine (1a, 38.8 mg, 0.2 mmol), NH4SCN (2a, 30.5 mg, 0.4 mmol, 2 equiv), Bu4NPF6 (194 mg, 0.5 mmol, 2.5 equiv), and MeCN (10 mL). The flask was equipped with two platinum plate electrodes (10 × 10 mm) as the anode and cathode, respectively. The reaction mixture was electrolyzed and stirred at a constant current (5 mA) under air at r.t. for 6 h. When the reaction was complete, the mixture was diluted with H2O (30 mL) and extracted with CH2Cl2 (3 × 10 mL). The combined organic phases were dried (Na2SO4), filtered, and concentrated in vacuo. The resulting crude product was purified by chromatography [silica gel, PE–EtOAc (5:1)] to give a white solid; yield: 42.7 mg (85%); mp 115–117 °C. 1H NMR (400 MHz, CDCl3): δ = 8.48 (d, J = 6.6 Hz, 1 H), 8.08 (d, J = 7.3 Hz, 2 H), 7.80 (d, J = 8.9 Hz, 1 H), 7.58–7.48 (m, 4 H), 7.16 (t, J = 6.7 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 153.0, 147.9, 131.9, 129.5, 128.8, 128.8, 128.1, 124.4, 118.3, 114.5, 108.2, 94.7.