Electrochemical Oxidative C—H Trifluoromethylation of Quinoxalin-2(1H)-ones and the Performance Evaluation via Electro-descriptors

doi:10.6023/cjoc202108023

Abstract

An operationally simple electrochemical oxidative C—H trifluoromethylation of quinoxalin-2(1H)-ones was achieved by employing the inexpensive, readily available and easy processing CF₃SO₂Na as CF₃ source. In the absence of any catalysts or oxidant reagents, this method is more in line with the requirements of green and sustainable development. Most importantly, “electric-descriptor-diagram” was used to evaluate the reaction substrates. The reactive/non-reactive boundary and the trend of yield change can been clearly seen.

Key words: qinoxalin-2(1H)-ones, electrochemical synthesis, trifluoromethylation, sodium trifluoromethanesulfinate, electro-descriptors

Cite this article

Xiaolong Guo, Yuxian Wang, Zhiqiang Zhao, Qing Wang, Jian Zuo, Luyao Wang. Electrochemical Oxidative C—H Trifluoromethylation of Quinoxalin-2(1H)-ones and the Performance Evaluation via Electro-descriptors[J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 641-649.

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Fig. & Tab. 6

Scheme 1. Methods for trifluoromethylation of quinoxalin- 2(1H)-ones

Entry	Variation from the standard reaction conditions	Yield^b/%
1	None	81
2	No H₂O and HOAc	30
3	No HOAc	53
4	No H₂O	46
5	DMF instead of CH₃CN	Trace
6	ⁿBu₄NPF₆, TBAI and TBAB instead of ⁿBu₄NBF₄	61, 0, 19
7	Pt, RVC instead of C as anode	44, 0
8	10 mA, 8 h instead of 20 mA, 4 h	77
9	30 mA, 3 h instead of 20 mA, 4 h	65
10	No electricity	0

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scope and electro-descriptors of different substrates under optimized conditionsa

Scheme 2. Mechanism experiment and radical trapping

Scheme 3. Possible reaction mechanism of electrochemical oxidative C—H trifluoromethylation

Figure 1. (a) Three electro-descriptors, onset potential, Tafel slope and effective voltage, identified from the CV diagram of Entries 26 and 28; (b) the 3D electro-descriptor-diagram built with three electro-descriptors

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