可见光介导下钯催化脂肪族α-溴代三氟甲基的脱溴还原反应

doi:10.6023/cjoc202406023

摘要/Abstract

三氟甲基因其特殊的理化性质在药物化学、材料科学等领域有着广泛的应用, 因此合成连有三氟甲基的有机物受到了广泛的关注. 然而, 目前对于脂肪族三氟甲基化合物的构建方法依然十分有限. 此工作以α-溴代三氟甲基化合物为原料, Pd(PPh₃)₄为催化剂, 在可见光介导下实现了烷基α-三氟甲基溴化物的脱溴还原, 生成一系列结构多样的三氟甲基烷基化产物.

关键词: 可见光介导, 钯催化, α-溴代三氟甲基化合物, 脱溴还原反应

Due to its unique physicochemical properties, the trifluoromethyl group has been widely used in medicinal chemistry and materials science. Thus, the synthesis of organic compounds bearing trifluoromethyl groups has attracted considerable attention. However, the current methods for constructing aliphatic trifluoromethyl compounds are still very limited. In this paper, α-bromotrifluoromethyl compounds were used as raw materials and Pd(PPh₃)₄ was used as catalyst to achieve the hydrodebromination of alkyl α-trifluoromethyl bromides under visible light irradiation, generating a series of structurally diverse trifluoromethylated alkanes.

Key words: visible light mediated, palladium-catalyzed, α-bromotrifluoromethyl compounds, hydrodebromination

引用此文

区洁晴, 屈培珍, 赵亮. 可见光介导下钯催化脂肪族α-溴代三氟甲基的脱溴还原反应[J]. 有机化学, 2025, 45(4): 1334-1341.

Jieqing Ou, Peizhen Qu, Liang Zhao. Visible Light Mediated Palladium-Catalyzed Hydrodebromination of Aliphatic α-Bromotrifluoromethyl Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1334-1341.

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图/表 5

图1. 2023年FDA批准的含三氟甲基烷基结构的药物

Figure 1. FDA-approved drugs containing trifluoromethylalkyl structures in 2023

图式1. α-溴代三氟甲基的脱溴还原策略

Scheme 1. Recent strategies to hydrodehalogenation of α- bromotrifluoromethyl

Entry	Pd(PPh₃)₄(x mol%)	Base	Solvent	Yield^b/%
1	5.0	K₂CO₃	THF	97 (95)
2	2.5	K₂CO₃	THF	76
3	1.0	K₂CO₃	THF	7
4	2.5	Cs₂CO₃	THF	63
5	2.5	KOAc	THF	92 (84)
6	2.5	K₃PO₄	THF	64
7	2.5	KHCO₃	THF	41
8	2.5	KOAc	MeOH	15
9	2.5	KOAc	DCM	—
10	2.5	KOAc	DMSO	19
11	2.5	KOAc	1,4-Dioxane	47
12	2.5	—	THF	Trace
13^c	2.5	KOAc	THF	Trace
14	—	KOAc	THF	—
15^d	2.5	KOAc	THF	72

表1. 反应条件优化的代表性结果a,b

Table 1. Representative results for the optimization of reaction conditions

表2. 底物普适性考察a,b

Table 2. Study on the substrate scope

图式2. 反应机理研究

Scheme 2. Reaction mechanism research

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