钯催化溴代芳烃邻位碳氢胺化/碳氢芳基化关环反应合成官能化氮杂䓬酮和菲啶

doi:10.6023/cjoc202502018

有机化学 ›› 2025, Vol. 45 ›› Issue (8): 2825-2835.DOI: 10.6023/cjoc202502018 上一篇下一篇

研究论文

钯催化溴代芳烃邻位碳氢胺化/碳氢芳基化关环反应合成官能化氮杂䓬酮和菲啶

陶星慧, 郭凯悦, 张继坦, 谢美华^*(), 吴佳萍^*()

安徽师范大学化学与材料科学学院功能分子固体教育部重点实验室分子基材料安徽省重点实验室中国芜湖 241002

收稿日期:2025-02-18 修回日期:2025-04-18 发布日期:2025-05-06
基金资助:
安徽省自然科学基金(2208085MB23); 安徽省自然科学基金(2108085MB60); 安徽省高等学校自然科学研究基金(2022AH050206); 安徽省高等学校自然科学研究基金(2023AH040028); 以及安徽师范大学本科创新实验(202310370024); 以及安徽师范大学本科创新实验(202410370037)

Synthesis of Functionalized Azepinones and Phenanthridines via a Pd-Catalyzed ortho-C—H Amination/C—H Arylation Cyclization Cascade of Aryl Bromides

Xinghui Tao, Kaiyue Guo, Jitan Zhang, Meihua Xie^*(), Jiaping Wu^*()

Anhui Key Laboratory of Molecular Based Materials, Key Laboratory of Functional Molecular Solids (Ministry of Education), College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241002

Received:2025-02-18 Revised:2025-04-18 Published:2025-05-06
Contact: *E-mail:wujiaping@ahnu.edu.cn;xiemh@mail.ahnu.edu.cn
Supported by:
Natural Science Foundation of Anhui Province(2208085MB23); Natural Science Foundation of Anhui Province(2108085MB60); Scientific Research Foundation of the Higher Education Institutions of Anhui Province(2022AH050206); Scientific Research Foundation of the Higher Education Institutions of Anhui Province(2023AH040028); Innovative Project for Undergraduates at Anhui Normal University(202310370024); Innovative Project for Undergraduates at Anhui Normal University(202410370037)

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摘要/Abstract

溴代芳胺和O-酰基羟胺酯通过Catellani催化策略, 实现二苯基氮杂䓬酮和菲啶骨架的简捷高效构建. 反应经历邻位碳氢胺化/分子内跨环碳氢芳基化串联历程, 且可以兼容一系列芳基溴代物和胺类化合物. 另外, 开展了菲啶产物光学性质的初步探究, 以期发掘该方法在新型荧光材料合成方面的潜在应用.

关键词: 氮杂䓬酮, 菲啶, 碳氢键活化, Catellani策略, 碳氢胺化

An expeditious access to dibenzoazepinone and phenanthridine scaffold enabled by a Catellani strategy from bromoarylamine and O-benzoylhydroxylamines is disclosed. This reaction proceeds smoothly involving an ortho-C—H amination/interannular C—H arylation cascade and well tolerates a number of aryl bromides and amine substrates. Furthermore, the preliminary study of photophysical properties of the synthesized pyrrolophenanthridine derivatives was also performed to explore the potential of this method for discovering novel photoelectric materials.

Key words: azepinones, phenanthridines, C—H activation, Catellani strategy, C—H amination

引用此文

陶星慧, 郭凯悦, 张继坦, 谢美华, 吴佳萍. 钯催化溴代芳烃邻位碳氢胺化/碳氢芳基化关环反应合成官能化氮杂䓬酮和菲啶[J]. 有机化学, 2025, 45(8): 2825-2835.

Xinghui Tao, Kaiyue Guo, Jitan Zhang, Meihua Xie, Jiaping Wu. Synthesis of Functionalized Azepinones and Phenanthridines via a Pd-Catalyzed ortho-C—H Amination/C—H Arylation Cyclization Cascade of Aryl Bromides[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2825-2835.

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图/表 8

图1. 重要氮杂䓬酮及啡啶稠环化合物

Figure 1. Important azepinone- and phenanthridine-fused heterocycles

图式1. 官能化氮杂䓬酮和啡啶化合物的合成

Scheme 1. Synthesis of functionalized azepinones and phenanthridines

Entry	[Pd]	Base	Ligand	Solvent	Temp./℃	Yield^b/%
1	Pd(OAc)₂	Cs₂CO₃	PPh₃	Toluene	80	23
2	Pd(PPh₃)₄	Cs₂CO₃	PPh₃	Toluene	80	31
3	Pd₂(dba)₃	Cs₂CO₃	PPh₃	Toluene	80	10
4	Pd(TFA)₂	Cs₂CO₃	PPh₃	Toluene	80	43
5	PdCl₂(PPh₃)₂	Cs₂CO₃	PPh₃	Toluene	80	21
6	Pd(TFA)₂	K₃PO₄	PPh₃	Toluene	80	12
7	Pd(TFA)₂	t-BuOK	PPh₃	Toluene	80	15
8	Pd(TFA)₂	K₂CO₃	PPh₃	Toluene	80	10
9	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	Toluene	80	59
10	Pd(TFA)₂	Cs₂CO₃	S-Phos	Toluene	80	23
11	Pd(TFA)₂	Cs₂CO₃	DPPB	Toluene	80	18
12	Pd(TFA)₂	Cs₂CO₃	DPPE	Toluene	80	14
13	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	DME	80	72
14	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	THF	80	32
15	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	DMF	80	29
16	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	Dioxane	80	40
17	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	o-Xylene	80	17
18	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	DME	60	53
19	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	DME	90	65
20	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	DME	100	63
21^c	Pd(TFA)₂	Cs₂CO₃	P(o-MeOC₆H₄)₃	DME	80	88

表1. 反应条件优化a

Table 1. Optimization of reaction conditionsa

表2. 底物拓展a,b

Table 2. Substrate scope

表3. 官能化菲啶的合成a,b

Table 3. Synthesis of functionalized phenanthridines

图式2. 放大反应及产物转化

Scheme 2. Gram-scale reaction and transformation of product

图2. 发光性质探究

Figure 2. Investigation of luminescent properties (a) Normalized absorption spectra of compounds 5ca, 5da, 5ga, and 5qa in ethyl acetate (EA) at room temperature. Inset: Photographs of compounds 5ca, 5da, 5ga, and 5qa in EA at room temperature (10－5 mol/L). (b) Normalized photoluminescence spectra of compounds 5ca, 5da, 5ga, and 5qa in EA at room temperature. Inset: Photographs of compounds 5ca, 5da, 5ga, and 5qa in EA at room temperature (10－5 mol/L), while photoexcited with a UV lamp (λex=365 nm).

图式3. 推测机理

Scheme 3. Proposed mechanism

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钯催化溴代芳烃邻位碳氢胺化/碳氢芳基化关环反应合成官能化氮杂䓬酮和菲啶

Synthesis of Functionalized Azepinones and Phenanthridines via a Pd-Catalyzed ortho-C—H Amination/C—H Arylation Cyclization Cascade of Aryl Bromides

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