三重协同催化杂芳烃与醛的脱羰芳基化/烷基化反应

doi:10.1016/S1872-2067(26)65170-4

催化学报 ›› 2026, Vol. 89: 422-429.DOI: 10.1016/S1872-2067(26)65170-4

三重协同催化杂芳烃与醛的脱羰芳基化/烷基化反应

文延萃^a, 曾飞^b, 谭誉宇^a, 易荣楠^c, 蒋俊^a, 伍智林^a, 彭俊梅^a, 唐裕才^d^,^e, 何卫民^a^,^*()

^a南华大学化学化工学院,湖南衡阳 421001
^b湘南学院药学院,湖南郴州 423099
^c湖南警察学院湖南省高校食品环境与药品监测与检测重点实验室,湖南长沙 410138
^d湖南文理学院化学与材料工程学院,湖南常德 415000
^e长沙医学院功能核酸基础与临床研究湖南省高校重点实验室,湖南长沙 410219

收稿日期:2025-10-28 接受日期:2026-03-02 出版日期:2026-10-18 发布日期:2026-09-01
通讯作者: *电子信箱: weiminhe@usc.edu.cn (何卫民).

Decarbonylative arylation/alkylation of heteroarenes with aldehydes via triplet synergistic catalysis

Yan-Cui Wen^a, Fei Zeng^b, Yu-Yu Tan^a, Rong-Nan Yi^c, Jun Jiang^a, Zhi-Lin Wu^a, Jun-Mei Peng^a, Yu-Cai Tang^d^,^e, Wei-Min He^a^,^*()

^aSchool of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, Hunan, China
^bCollege of Pharmacy, Xiangnan University, Chenzhou 423099, Hunan, China
^cKey Laboratory of Food & Environment & Drug Monitoring and Testing of Universities in Hunan Province, Hunan Police Academy, Changsha 410138, Hunan, China
^dCollege of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde 415000, Hunan, China
^eHunan Provincial University Key Laboratory of the Fundamental and Clinical Research on Functional Nucleic Acid, Changsha Medical University, Changsha 410219, China

Received:2025-10-28 Accepted:2026-03-02 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:weiminhe@usc.edu.cn(W.-M. He).

摘要/Abstract

摘要：

杂芳烃是天然产物、合成药物及生物活性化合物中的核心结构单元. 因此, 从廉价易得的大宗原料出发, 发展可持续的合成路线用于制备高附加值官能化的杂芳烃, 一直是有机合成领域的重要目标. 由于芳香醛的Ar‒C(O)键解离能较高, 其光催化脱羰芳基化反应仍面临重大挑战, 且传统脱羰策略大多局限于烷基醛难以实现芳香醛的温和转化. 因此, 开发基于醛类原料的杂芳烃脱羰芳基化新方法, 对推动有机合成与药物化学的绿色可持续发展具有重要意义.

本研究提出一种融合光诱导氢原子转移、光氧化还原与氢键有机催化的三重协同光催化策略, 在无金属、无强氧化剂的温和条件下, 成功实现了杂芳烃与醛的脱羰芳基化/烷基化反应. 曙红Y在反应中同时承担光诱导氢原子转移与光氧化还原双重催化功能. 以N-甲基喹喔啉-2(1H)-酮与苯甲醛为模型反应进行条件优化, 筛选出曙红Y为最优光催化剂、三氟乙酸为最优氢键催化剂、二茂铁为氧化还原催化剂, 在455 nm蓝光照射下目标产物收率达88%, 且氧气和光照为反应必需条件. 底物拓展实验表明, 该体系具有广泛的底物兼容性: 各类取代的喹喔啉-2(1H)-酮及其他N/O-杂芳烃均能顺利反应; 芳香醛、烷基醛、烯醛以及天然产物和药物衍生醛也能有效参与, 共合成47个芳基化/烷基化杂芳烃衍生物, 多数收率良好. 机理研究表明, 三氟乙酸与醛之间形成的氢键复合物是降低脱羰能垒的关键. 密度泛函理论计算显示, 该氢键作用可使苯甲酰自由基的C‒C(O)键断裂能垒从21.47 kcal/mol降至19.08 kcal/mol. 核磁滴定、循环伏安及荧光猝灭实验进一步证实了氢键相互作用的存在. 通过活性物种探究实验发现反应涉及自由基路径, 超氧自由基阴离子与氢过氧自由基为关键活性物种, 且单电子转移过程是不可或缺的. 基于上述结果, 提出合理反应机理: 三氟乙酸与醛形成氢键复合物后, 经激发态曙红Y攫取氢原子, 生成酰基自由基, 该自由基进一步脱羰形成碳自由基, 并选择性加成至杂芳烃; 所得自由基中间体经1,2-氢迁移后, 在二茂铁的作用下通过单电子氧化过程脱氢芳构化, 最终得到目标产物.

综上, 本研究发展的三重协同催化体系为杂芳烃的高效官能团化提供了新方法, 实现了醛类可再生资源的光催化高值化利用, 也为多重协同催化在有机合成中的设计与应用提供了新范例. 该策略条件温和、无需金属催化剂, 符合绿色化学与可持续发展的要求, 有望在复杂分子的后期修饰及药物合成领域获得广泛应用.

关键词: 氢键有机催化, 醛, 脱羰基烷基化, 三重协同催化, 可见光

Abstract:

The development of sustainable synthetic routes from aldehydes to functionalized heteroarenes is an important goal in organic synthesis, owing to the low cost and ready accessibility of aldehydes. However, the high bond dissociation energy (BDE) of the Ar-C(O) bond makes the photocatalytic decarbonylative arylation of heteroarenes a formidable challenge. Herein, we report a novel photocatalytic strategy integrating photoinduced-hydrogen atom transfer (photo-HAT), photoredox, and hydrogen-bonding (HB) organocatalysis for the decarbonylative arylation/alkylation of heteroarenes using aldehydes. This method exhibits broad substrate scope across diverse heteroarenes and aldehydes, delivering products in high yields without metals or strong oxidants. Mechanistic studies show that HB-complexation between aldehydes and TFA is crucial for lowering the decarbonylation barrier. Eosin Y acts as a dual photo-HAT/photoredox catalyst, simplifying the system, while ferrocene promotes oxidative dehydroaromatization.

Key words: Hydrogen-bonding organocatalysis, Aldehydes, Decarbonylative alkylation, Triplet synergistic catalysis, Visible light

文延萃, 曾飞, 谭誉宇, 易荣楠, 蒋俊, 伍智林, 彭俊梅, 唐裕才, 何卫民. 三重协同催化杂芳烃与醛的脱羰芳基化/烷基化反应[J]. 催化学报, 2026, 89: 422-429.

Yan-Cui Wen, Fei Zeng, Yu-Yu Tan, Rong-Nan Yi, Jun Jiang, Zhi-Lin Wu, Jun-Mei Peng, Yu-Cai Tang, Wei-Min He. Decarbonylative arylation/alkylation of heteroarenes with aldehydes via triplet synergistic catalysis[J]. Chinese Journal of Catalysis, 2026, 89: 422-429.

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三重协同催化杂芳烃与醛的脱羰芳基化/烷基化反应

Decarbonylative arylation/alkylation of heteroarenes with aldehydes via triplet synergistic catalysis

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Metrics

Entry	Photocata.	Acid	Redox cata.	Time (h)	Yield ^b(%)
1	w/o	w/o	w/o	30	16
2	Eosin Y	w/o	w/o	30	29
3	Eosin B	w/o	w/o	30	25
4	Rhodamine 6G	w/o	w/o	30	27
5	4CzIPN	w/o	w/o	30	20
6	fac-Ir(ppy)₃	w/o	w/o	30	19
7	Ru(bpy)₃Cl₂	w/o	w/o	30	trace
8	Eosin Y	TFA	w/o	8	67
9	Eosin Y	TCA	w/o	8	61
10	Eosin Y	AcOH	w/o	8	58
11	Eosin Y	HCO₂H	w/o	8	51
12	Eosin Y	TFA	Cp₂Fe	8	88
13	Eosin Y	TFA	NHPI	8	82
14	Eosin Y	TFA	Ph₃N	8	69
15	Eosin Y	TFA	Fluorene	8	77
16	Eosin Y	TFA	DDQ	8	62
17^c	Eosin Y	TFA	Cp₂Fe	8	63
18^d	Eosin Y	TFA	Cp₂Fe	8	72
19^e	Eosin Y	TFA	Cp₂Fe	8	44
20	w/o	w/o	Cp₂Fe	30	25
21	w/o	TFA	w/o	8	47
22^f	Eosin Y	TFA	Cp₂Fe	30	N.R.
23^g	Eosin Y	TFA	Cp₂Fe	30	N.R.

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