Intramolecular Charge Transfer Complex Enabled Trifluoromethylation of Heteroarenes with Trifluoromethyl Phosphonium Salt

doi:10.6023/cjoc202411006

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (7): 2545-2551.DOI: 10.6023/cjoc202411006 Previous Articles Next Articles

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三氟甲基鏻盐分子内电荷转移复合物促使的杂芳烃三氟甲基化反应

刘帅^a^,^c^,^†, 陈坤泉^b^,^†, 孙德群^a^,^*(), 刘强^c^,^*(), 陈祥雨^c^,^*()

^a 西南科技大学生命科学与工程学院四川绵阳 621010
^b 莆田学院药学与医学技术学院医学微生态重点实验室福建莆田 351100
^c 中国科学院大学化学科学学院北京 100049

收稿日期:2024-11-06 修回日期:2024-12-30 发布日期:2025-01-24
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22101279); 中央高校基础科研资助项目和北京分子科学国家实验室(BNLMS2023014)

Intramolecular Charge Transfer Complex Enabled Trifluoromethylation of Heteroarenes with Trifluoromethyl Phosphonium Salt

Shuai Liu^a^,^c, Kunquan Chen^b, Dequn Sun^a^,^*(), Qiang Liu^c^,^*(), Xiangyu Chen^c^,^*()

^a School of Life Science and Engineering, Southwest University of Science and Technology, Mianyang, Sichuan 621010
^b Key Laboratory of Medical Microecology, School of Pharmacy and Medical Technology, Putian University, Putian, Fujian 351100
^c School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049

Received:2024-11-06 Revised:2024-12-30 Published:2025-01-24
Contact: *E-mail: dqsun@swust.edu.cn; liuqiang@ucas.ac.cn; chenxiangyu20@ucas.ac.cn
About author:
^† The authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(22101279); Fundamental Research Funds for the Central Universities and the Beijing National Laboratory for Molecular Sciences(BNLMS2023014)

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Abstract

A photoinduced intramolecular charge transfer complex (ICTC)-enabled photoreduction of trifluoromethyl phosphonium salt for the trifluoromethylation of heteroarenes was developed. It offers a convenient approach to introduce trifluoromethyl group to a wide range of aromatic heterocycles, such as indoles, pyrrole, substituted benzene, coumarin, and chromone. This strategy provides operational simplicity, photocatalyst-, transition metal-, and oxidant-free conditions, making it highly advantageous.

Key words: trifluoromethyl phosphonium salt, charge transfer complex, trifluoromethylation, photoinduced

Cite this article

Shuai Liu, Kunquan Chen, Dequn Sun, Qiang Liu, Xiangyu Chen. Intramolecular Charge Transfer Complex Enabled Trifluoromethylation of Heteroarenes with Trifluoromethyl Phosphonium Salt[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2545-2551.

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Fig. & Tab. 5

Figure 1. (A) Traditional methods to access trifluoromethyl heteroarenes, (B) photoinduced direct trifluoromethylation of heteroarenes, (C) our previous development, (D) ICTC-enabled direct trifluoromethylation of heteroarenes (this work)

Entry	Solvent	Base	Yield^b/%
1	DMA	—	57
2	DMA	KHCO₃	50
3	DMA	K₂CO₃	52
4	DMA	Cs₂CO₃	53
5	DMA	^tBuOK	Trace
6	DMA	K₃PO₄	Trace
7	DMA	NEt₃	78
8	DMA	DBU	63
9	DMA	TMEDA	72
10	DMA	DABCO	Trace
11	DMF	NEt₃	47
12	DMSO	NEt₃	32
13	DCM	NEt₃	60
14	MeCN	NEt₃	46
15	THF	NEt₃	Trace
16^c	DMA	NEt₃	82 (78)^d
17^c^,^e	DMA	NEt₃	NR

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scopea,b

Figure 2. Mechanistic studies

Figure 3. Possible mechanism

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三氟甲基鏻盐分子内电荷转移复合物促使的杂芳烃三氟甲基化反应

Intramolecular Charge Transfer Complex Enabled Trifluoromethylation of Heteroarenes with Trifluoromethyl Phosphonium Salt

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