可见光驱动CF3Br与未活化烯烃的溴-三氟甲基化反应研究

doi:10.6023/cjoc202604019

摘要/Abstract

以fac-Ir^III(ppy)₃为光催化剂, 实现了可见光驱动CF₃Br与未活化烯烃的溴-三氟甲基化反应. 在反应中, CF₃Br作为双功能试剂, 可同时提供三氟甲基源与溴源. 该方法具有区域选择性高、反应条件温和、原子利用率高、产率良好等特点, 为构建结构多样的β-三氟甲基溴代烃提供了一种经济实用的新方法.

关键词: 可见光驱动, CF₃Br, 未活化烯烃, 溴-三氟甲基化, 双功能三氟甲基试剂

A visible-light promoted bromotrifluoromethylation reaction of CF₃Br with unactivated alkenes was achieved in the presence of catalytic amount of fac-Ir^III(ppy)₃. In the reaction, CF₃Br serves as a bifunctional reagent to provide both the CF₃ group and bromine source. The method features high regioselectivity, mild reaction conditions, high atom economy and good yields, which offers an economical and practical method for the construction of structurally diverse β-trifluoromethylated alkyl bromides.

Key words: visible-light promotion, CF₃Br, unactivated alkenes, bromotrifluoromethylation, bifunctional trifluoromethylating reagents

引用此文

赵明琪, 黄丹凤, 温欢, 张丹, 王克虎, 王君姣, 张博生, 胡雨来. 可见光驱动CF₃Br与未活化烯烃的溴-三氟甲基化反应研究[J]. 有机化学, 2026, 46(9): 3603-3614.

Mingqi Zhao, Danfeng Huang, Huan Wen, Dan Zhang, Kehu Wang, Junjiao Wang, Bosheng Zhang, Yulai Hu. Visible-Light Promoted Bromotrifluoromethylation Reaction of CF₃Br with Unactivated Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3603-3614.

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图/表 10

图式1. 可见光驱动下烯烃的卤-三氟甲基化反应

Scheme 1. Visible-light-promoted halotrifluoromethylation reaction of alkenes

图式2. CF3Br与烯烃的双官能团化反应

Scheme 2. Difunctionalization of CF3Br with alkenes

Entry	n(alkenes)/n(base)	Base	Solvent	Isolated yield/%
1	1.0/1.0	K₂CO₃	MeCN	61
2	1.0/1.5	K₂CO₃	MeCN	71
3	1.0/2.0	K₂CO₃	MeCN	96
4	1.0/2.5	K₂CO₃	MeCN	69
5^b	1.0/2.0	K₂CO₃	MeCN	82
6^c	1.0/2.0	K₂CO₃	MeCN	71
7^d	1.0/2.0	K₂CO₃	MeCN	84
8^e	1.0/2.0	K₂CO₃	MeCN	62
9	1.0/2.0	K₂CO₃	DMSO	N.R.^f
10	1.0/2.0	K₂CO₃	Acetone	48
11	1.0/2.0	K₂CO₃	DCM	N.R.
12	1.0/2.0	K₂CO₃	EtOAc	Trace
13	1.0/2.0	K₂CO₃	THF	22
14	1.0/2.0	K₂CO₃	1,4-Dioxane	Trace
15	1.0/2.0	Na₂CO₃	MeCN	87
16	1.0/2.0	NaHCO₃	MeCN	90
17	1.0/2.0	K₂HPO₄	MeCN	90
18	1.0/2.0	K₃PO₄	MeCN	76
19	1.0/2.0	DBU	MeCN	N.R.
20	1.0/2.0	TMEDA	MeCN	N.R.
21^g	1.0/2.0	K₂CO₃	MeCN	83
22^h	1.0/0.0	—	MeCN	7
23ⁱ	1.0/2.0	K₂CO₃	MeCN	N.R.
24^j	1.0/2.0	K₂CO₃	MeCN	N.R.

表1. CF3Br与4-戊烯基苯甲酸酯的溴-三氟甲基化的反应条件优化a

Table 1. Optimization of conditions for the bromotrifluoromethylation of CF3Br with 4-pentenyl benzoate

表2. 未活化烯烃的范围a

Table 2. Scope of unactivated alkenes

图1. 含有烯键官能团的生物活性化合物的应用

Figure 1. Application to biologically active compounds containing an alkene functional group

图式3. 克级规模反应

Scheme 3. Gram-scale reaction

图式4. 自由基捕获实验及自由基钟实验

Scheme 4. Radical trapping experiment and radical clock experiment

图2. 开关灯实验

Figure 2. On/off light experiment

图式5. 卤素竞争实验

Scheme 5. Halogen competition experiment

图式6. 可见光驱动CF3Br与未活化烯烃的溴-三氟甲基化反应可能的反应机理

Scheme 6. A possible reaction mechanism of bromotrifluoromethylation of CF3Br with unactivated alkenes promoted by visible light

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可见光驱动CF₃Br与未活化烯烃的溴-三氟甲基化反应研究

Visible-Light Promoted Bromotrifluoromethylation Reaction of CF₃Br with Unactivated Alkenes

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