Photosensitizer-Free Photoinduced Hydrodifluoroalkylation of α‑Trifluoromethyl Alkenes

doi:10.6023/cjoc202507014

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (2): 641-652.DOI: 10.6023/cjoc202507014 Previous Articles Next Articles

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无光敏剂光诱导α-三氟甲基烯烃的氢二氟烷基化反应

范润东^a, 陈冰然^a, 黎富奇^a, 陈锦秀^a, 严琼姣^a^,^*(), 汪伟^b^,^*(), 周慧^b^,^*()

^a 武汉工程大学药物研究院武汉 430205
^b 华中师范大学化学学院武汉 430079

收稿日期:2025-07-11 修回日期:2025-09-05 发布日期:2025-10-09
通讯作者: 严琼姣, 汪伟, 周慧
基金资助:
湖北省自然科学基金(2025AFB675); 湖北省重点研发计划(2023BCB055)

Photosensitizer-Free Photoinduced Hydrodifluoroalkylation of α‑Trifluoromethyl Alkenes

Rundong Fan^a, Bingran Chen^a, Fuqi Li^a, Jinxiu Chen^a, Qiongjiao Yan^a^,^*(), Wei Wang^b^,^*(), Hui Zhou^b^,^*()

^a Pharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205
^b Department of Chemistry, Central China Normal University, Wuhan 430079

Received:2025-07-11 Revised:2025-09-05 Published:2025-10-09
Contact: Qiongjiao Yan, Wei Wang, Hui Zhou
Supported by:
Natural Science Foundation of Hubei Province(2025AFB675); Key Research and Development Program of Hubei Province(2023BCB055)

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Abstract

Photoinduced hydrodifluoroalkylation of α‑trifluoromethyl alkenes with bromodifluoride reagents has been accomplished using a Hantzsch ester as an electron donor and hydrogen source. This transformation proceeded smoothly in the absence of photocatalyst and transition metal, affording a series of trifluoromethylated difluoroacetates and difluoroacetamides in moderate to good yields. This catalytic system exhibits a broad substrate scope and high functional group tolerance, successfully accommodating structurally complex substrates including natural product derivatives.

Key words: α‑trifluoromethyl alkenes, bromodifluoride reagents, Hantzsch esters, hydrodifluoroalkylation, photoinduced

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Rundong Fan, Bingran Chen, Fuqi Li, Jinxiu Chen, Qiongjiao Yan, Wei Wang, Hui Zhou. Photosensitizer-Free Photoinduced Hydrodifluoroalkylation of α‑Trifluoromethyl Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 641-652.

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References 7

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Entry	Reductant	Light source	Solvent	Yield^b/%
1	HE	365 nm	CH₃CN	42
2	Et₃N	365 nm	CH₃CN	—
3	TMEDA	365 nm	CH₃CN	—
4	Bn₃N	365 nm	CH₃CN	—
5	PMDETA	365 nm	CH₃CN	—
6	HE	365 nm	CH₂Cl₂	69
7	HE	365 nm	EtOAc	69
8	HE	365 nm	1,4-Dioxane	57
9	HE	365 nm	THF	59
10	HE	365 nm	2-MeTHF	57
11	HE	365 nm	CH₃OH	90
12	HE	400 nm	CH₃OH	80
13	HE	460 nm	CH₃OH	56
14	HE	white LEDs	CH₃OH	60
15	HE	—	CH₃OH	—
16	—	365 nm	CH₃OH	—

Entry	Reductant	Light source	Solvent	Yield^b/%
1	HE	365 nm	CH₃CN	42
2	Et₃N	365 nm	CH₃CN	—
3	TMEDA	365 nm	CH₃CN	—
4	Bn₃N	365 nm	CH₃CN	—
5	PMDETA	365 nm	CH₃CN	—
6	HE	365 nm	CH₂Cl₂	69
7	HE	365 nm	EtOAc	69
8	HE	365 nm	1,4-Dioxane	57
9	HE	365 nm	THF	59
10	HE	365 nm	2-MeTHF	57
11	HE	365 nm	CH₃OH	90
12	HE	400 nm	CH₃OH	80
13	HE	460 nm	CH₃OH	56
14	HE	white LEDs	CH₃OH	60
15	HE	—	CH₃OH	—
16	—	365 nm	CH₃OH	—

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无光敏剂光诱导α-三氟甲基烯烃的氢二氟烷基化反应

Photosensitizer-Free Photoinduced Hydrodifluoroalkylation of α‑Trifluoromethyl Alkenes

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