可见光介导下铱催化脂肪族α-溴代三氟甲基的脱溴环化反应

doi:10.6023/cjoc202409018

有机化学 ›› 2025, Vol. 45 ›› Issue (7): 2520-2528.DOI: 10.6023/cjoc202409018 上一篇下一篇

研究论文

可见光介导下铱催化脂肪族α-溴代三氟甲基的脱溴环化反应

毛婷, 曾鳞媛, 温吉林, 贾佳^*()

遵义医科大学贵州省生物催化与手性药物合成重点实验室贵州遵义 563000

收稿日期:2024-09-18 修回日期:2024-12-24 发布日期:2025-01-24
通讯作者: 贾佳
基金资助:
遵义市科技计划([2023]169); 贵州省科技计划([2021]1350-005); 贵州省科学技术厅(QKHPTRC-CXTD2022-012)

Visible Light-Mediated Iridium-Catalyzed Debromocyclization of Aliphatic α-Bromotrifluoromethyl Groups

Ting Mao, Linyuan Zeng, Jilin Wen, Jia Jia^*()

Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, Zunyi Medical University, Zunyi, Guizhou 563000

Received:2024-09-18 Revised:2024-12-24 Published:2025-01-24
Contact: Jia Jia
Supported by:
Science and Technology Plan Project of Zunyi City([2023]169); Science and Technology Plan Project of Guizhou Province([2021]1350-005); Science and Technology Department of Guizhou Province(QKHPTRC-CXTD2022-012)

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摘要/Abstract

四氢萘和三氟甲基是药物化学中常见的结构单元, 发展了一种三氟甲基四氢萘及其类似物的合成方法. 该方法使用α-三氟甲基溴化物为原料, 在可见光介导下以Ir(ppy)₃为光催化剂, 通过脱溴环化反应得到, 具有反应条件相对温和、官能团兼容性好及化学选择性好的优点.

关键词: 可见光介导, 铱催化, α-溴代三氟甲基化合物, 脱溴环化反应

Tetralin and trifluoromethyl are common structural units in medicinal chemistry. A method for the synthesis of trifluoromethyltetralin and its analogs was developed. The method using α-trifluoromethyl bromide as the raw material is obtained by debromination cyclization reaction mediated by visible light with Ir(ppy)₃ as photocatalyst, which has the advantages of relatively mild reaction conditions, good functional group compatibility and good chemoselectivity.

Key words: visible-light-mediation, iridium-catalysis, α-bromotrifluoromethyl compound, debromocyclization reaction

引用此文

毛婷, 曾鳞媛, 温吉林, 贾佳. 可见光介导下铱催化脂肪族α-溴代三氟甲基的脱溴环化反应[J]. 有机化学, 2025, 45(7): 2520-2528.

Ting Mao, Linyuan Zeng, Jilin Wen, Jia Jia. Visible Light-Mediated Iridium-Catalyzed Debromocyclization of Aliphatic α-Bromotrifluoromethyl Groups[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2520-2528.

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图/表 5

图1. 含四氢萘结构的药物

Figure 1. drugs containing tetralin structures

图式1. 烷基溴化物的脱溴环化策略

Scheme 1. Debromination cyclization strategies for alkyl bromides

Entry	Base	Solvent	Yield/%
1	DMAP	DMA	22
2	Et₃N	DMA	7
3	KOAc	DMA	37
4	Na₂CO₃	DMA	41
5	NaOAc	DMA	45
6	Na₂HPO₄	DMA	43
7	NaOAc	DMSO	43
8	NaOAc	THF	32
9	NaOAc	MeCN	25
10	NaOAc	MeOH	Trace
11	NaOAc	Toluene	56
12	NaOAc	DMF	45
13 (410~415 nm)	NaOAc	DMSO	78
14 (440~445 nm)	NaOAc	DMSO	86
15 (470~475 nm)	NaOAc	DMSO	87 (86)
16 (495~500 nm)	NaOAc	DMSO	66
17 (dark)	NaOAc	DMSO	—

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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可见光介导下铱催化脂肪族α-溴代三氟甲基的脱溴环化反应

Visible Light-Mediated Iridium-Catalyzed Debromocyclization of Aliphatic α-Bromotrifluoromethyl Groups

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