电化学氧化下喹喔啉-2(1H)-酮的三氟甲基化及电描述符对反应性能的评价

doi:10.6023/cjoc202108023

摘要/Abstract

通过使用廉价易得且易于处理的CF₃SO₂Na作为CF₃源, 实现了操作简单的电化学氧化喹喔啉-2(1H)-酮的C—H三氟甲基化. 由于没有使用任何催化剂或氧化剂, 该方法符合绿色和可持续发展的要求. 最重要的是, 使用“电描述符图”来评估底物的反应活性, 可以清楚地看到反应/非反应边界和产量变化趋势.

关键词: 喹喔啉-2(1H)-酮, 电化学合成, 三氟甲基化, 三氟甲基亚磺酸钠, 电化学描述符

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

引用此文

锅小龙, 王玉贤, 赵志强, 王庆, 左剑, 王陆瑶. 电化学氧化下喹喔啉-2(1H)-酮的三氟甲基化及电描述符对反应性能的评价[J]. 有机化学, 2022, 42(2): 641-649.

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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图/表 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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