基于催化量电子供体-受体复合物自由基接力选择性地实现烯烃氰烷基双官能化

doi:10.1016/S1872-2067(26)64995-9

催化学报 ›› 2026, Vol. 86: 244-253.DOI: 10.1016/S1872-2067(26)64995-9

基于催化量电子供体-受体复合物自由基接力选择性地实现烯烃氰烷基双官能化

李昊聪^a, 张明^a, 杨恒博^a, 陈晓岚^a^,^*(), 吕琪妍^a^,^c^,^*(), 屈凌波^a^,^b, 於兵^a^,^*()

^a 郑州大学化学学院（生命科学学院）, 河南郑州 450001
^b 河南省科学院化学研究所, 河南郑州 450002
^c 南京林业大学, 林木生物质低碳高效利用国家工程研究中心, 江苏南京 210037

收稿日期:2025-11-10 接受日期:2025-11-21 出版日期:2026-07-05 发布日期:2026-06-12
通讯作者: ^*电子信箱: chenxl@zzu.edu.cn (陈晓岚),
qiyanlv@zzu.edu.cn (吕琪妍),
bingyu@zzu.edu.cn (於兵).
基金资助:
国家自然科学基金(22071222);国家自然科学基金(22171249);111引智基地(D20003);河南省自然科学基金项目(242301420006);河南省自然科学基金项目(252300421245);河南科学院高层次人才研究启动项目(20251818003);中原科技创新青年拔尖人才.

Photocatalyst-free chemoselective radical-relay strategy enabled cyanoalkyl difunctionalization of alkenes via catalytic EDA complex

Hao-Cong Li^a, Ming Zhang^a, Heng-Bo Yang^a, Xiao-Lan Chen^a^,^*(), Qiyan Lv^a^,^c^,^*(), Lingbo Qu^a^,^b, Bing Yu^a^,^*()

^a College of Chemistry, School of Life Sciences, Zhengzhou University, Zhengzhou 450001, Henan, China
^b Institute of Chemistry, Henan Academy of Sciences, Zhengzhou 450002, Henan, China
^c National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2025-11-10 Accepted:2025-11-21 Online:2026-07-05 Published:2026-06-12
Supported by:
National Natural Science Foundation of China(22071222);National Natural Science Foundation of China(22171249);111 Project(D20003);Natural Science Foundation of Henan Province(242301420006);Natural Science Foundation of Henan Province(252300421245);High-level Talent Research Start-up Project Funding of Henan Academy of Sciences(20251818003);Zhongyuan Leading Young Talents in Scientific and Technological Innovation.

摘要/Abstract

摘要：

氰烷基是一类重要的结构单元, 广泛存在于天然产物和药物分子中. 近年来, 基于环酮肟酯衍生物产生氰烷基自由基的策略已成为构建氰烷基化合物的有效途径. 然而, 该类方法通常依赖高温条件或贵金属/有机染料光催化剂, 因而开发无需外加光催化剂的光催化氰烷基化方法具有重要研究意义. 电子供体-受体(EDA)复合物可在光照条件下诱导产生自由基, 无需额外光催化剂, 被认为是一种绿色环保的有机合成策略. 目前, EDA复合物的形成多依赖于化学计量的电子供体, 而采用催化量EDA的途径更具吸引力, 但仍面临诸多挑战: 首先, 现有催化量EDA体系中适用的自由基前体种类有限, 亟需拓展新型前体; 其次, 已报道的催化量EDA反应多集中于两组分反应, 而能够显著提升分子复杂性与多样性的多组分反应研究不足; 此外, 现有的三芳胺催化体系主要聚焦于杂原子-碳键的构建, 同时构建多个碳-碳键的反应鲜有报道.

本文发展了一种在催化量EDA复合物介导下通过自由基接力实现烯烃氰烷基双官能化的新策略. 该反应以三芳胺作为催化量的电子供体, 在可见光照射下高效构建了多个碳-碳键. 反应体系对多种氰烷基自由基前体及缺电子烯烃均表现出良好的兼容性. 特别值得指出的是, 以丙烯酸苄酯类衍生物为底物时, 可成功合成具有重要合成价值的1,4-二羰基化合物. 此外, 在绿色温和的反应条件下, 该方法还可高效构建双氰基及三氰基取代产物. 除氰烷基自由基外, 酰基自由基前体在该体系中也可顺利转化, 获得相应产物. 机理研究表明, 紫外-可见吸收光谱与¹⁹F核磁共振跟踪实验证实了EDA复合物的形成, 自由基捕获实验支持氰烷基自由基的生成; 动力学实验表明, 反应决速步为EDA复合物内的电子转移. 量子产率测定结果排除了自由基链式反应机制. 基于上述实验结果, 本文提出以下反应机理: 三芳胺与环酮全氟吡啶肟首先形成EDA复合物, 在光照下生成环酮全氟吡啶肟自由基阴离子中间体, 后者经氮-氧键断裂产生亚胺自由基. 该亚胺自由基通过β位碳-碳键断裂释放氰烷基自由基, 随后对缺电子烯烃进行自由基加成, 得到碳自由基中间体. 该中间体与烯醇硅醚反应生成更稳定的三级碳自由基, 最终被三芳胺自由基阳离子氧化, 脱除三甲基硅正离子, 得到目标产物.

综上, 本文发展了一种基于催化量EDA复合物的自由基接力的新策略, 成功实现了烯烃的氰烷基化双官能团化反应, 具备良好的化学选择性、底物适用性与官能团兼容性, 为基于EDA复合物的光诱导自由基反应设计与应用提供了新思路.

关键词: 催化量电子供体-受体复合物, 自由基接力, 三芳胺, 双官能团化, 氰烷基化

Abstract:

The electron donor-acceptor (EDA) strategy has emerged as a sustainable alternative in photochemistry, enabling the generation of radicals without any photocatalysts. However, the formation of the EDA complex often requires stoichiometric donors, resulting in excessive waste of the electron donors, and the catalytic EDA strategy remains challenging. Herein, a novel catalytic EDA complex, employing N-(4-bromophenyl)-N-phenylnaphthalen-1-amine as the catalytic electron donor and O-aryl oximes as electron acceptors, was described to achieve cyanoalkyl difunctionalization of alkenes via a radical-relay strategy under visible-light irradiation. Various versatile compounds with cyanoalkyl and 1,4-dicarbonyl groups could be easily synthesized under green and sustainable reaction conditions. The significance of this sustainable methodology was highlighted by the novel catalytic EDA complex, broad substrate scope (36 examples), green solvent, good synthetic applications, and high selectivity.

Key words: Catalytic electron donor-acceptor, Radical relay, Triarylamines, Difunctionalization, Cyanoalkylation

李昊聪, 张明, 杨恒博, 陈晓岚, 吕琪妍, 屈凌波, 於兵. 基于催化量电子供体-受体复合物自由基接力选择性地实现烯烃氰烷基双官能化[J]. 催化学报, 2026, 86: 244-253.

Hao-Cong Li, Ming Zhang, Heng-Bo Yang, Xiao-Lan Chen, Qiyan Lv, Lingbo Qu, Bing Yu. Photocatalyst-free chemoselective radical-relay strategy enabled cyanoalkyl difunctionalization of alkenes via catalytic EDA complex[J]. Chinese Journal of Catalysis, 2026, 86: 244-253.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)64995-9

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图/表 6

Fig. 1. Generation of cyanoalkyl radicals and overview of catalytic EDA system. (a) Traditional methods for generating cyanoalkyl radicals. (b) Catalytic EDA systems: examples of catalytic donors. (c) Reported catalytic EDA systems by triarylamine as a donor. (d) This work: Catalytic EDA-enabled multicomponent reaction.

Fig. 2. The optimization of reaction conditions. Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), 3a (0.25 mmol), donor (20 mol%), solvent (2 mL), 40 W blue Kessil LED lamp (427 nm), under N2 for 48 h. Isolated yields were given. (a) The optimization of solvents. (b) The optimization of electron donors. (c) Corresponding yields of electron donors. (d) The optimization of oxime esters. (e) The optimization of concentration. (f) Control experiments.

Table 1 Substrate scope a.

Fig. 3. (a) Scale-up synthesis of 4a. (b) Acyl difunctionalization of alkene. (c) Transformation of 4a. (d) Sensitivity assessment.

Fig. 4. Mechanistic studies. (a) Radical trapping experiments. (b) UV-Vis absorption spectra. (c) 19F NMR trapping experiments. (d) Job’s plot. (e) Kinetic experiments. (f) Time-correlated single-photon counting spectrum. (g) Molar absorption coefficient.

Fig. 5. Proposed mechanism.

参考文献

[1]	M. Yang, P. Cao, Chin. J. Org. Chem., 2023, 43, 1608-1609.
[2]	S. Wang, B. Jiang, Chin. J. Org. Chem., 2021, 41, 4531-4533.
[3]	R. López, C. Palomo, Angew. Chem. Int. Ed., 2015, 54, 13170-13184.
[4]	W. Xiao, J. Wu, Chin. Chem. Lett., 2020, 31, 3083-3094.
[5]	F. Xiao, Y. Guo, Y.-F. Zeng, Adv. Synth. Catal., 2021, 363, 120-143.
[6]	X.-Y. Yu, J.-R. Chen, W.-J. Xiao, Chem. Rev., 2021, 121, 506-561.
[7]	H. Ni, Y. Wang, K. Yao, L. Wang, J. Huang, Y. Xiao, H. Chen, B. Liu, C. Y. Yang, J. Zhao, Nat. Commun., 2024, 15, 1.
[8]	L. Ding, K. Niu, Y. Liu, Q. Wang, Chin. Chem. Lett., 2022, 33, 4057-4060.
[9]	L. Wang, Y. Zheng, X. Zhou, H. Wang, Q. Yan, W. Wang, F. Chen, Chin. J. Org. Chem., 2023, 43, 668-678.
[10]	K. A. Rykaczewski, E. R. Wearing, D. E. Blackmun, C. S. Schindler, Nat. Synth., 2022, 1, 24-36.
[11]	E. M. Dauncey, S. U. Dighe, J. J. Douglas, D. Leonori, Chem. Sci., 2019, 10, 7728-7733.
[12]	C. Peng, Y. Tang, S. Sun, Y. Wei, W. Zhou, L.-N. Guo, L. Xu, S. Liu, Org. Chem. Front., 2024, 11, 6104-6109.
[13]	J. Zhang, X. Li, W. Xie, S. Ye, J. Wu, Org. Lett., 2019, 21, 4950-4954.
[14]	W. Zhang, Y.-L. Pan, C. Yang, X. Li, B. Wang, Org. Chem. Front., 2019, 6, 2765-2770.
[15]	J. Chen, Y.-J. Liang, P.-Z. Wang, G.-Q. Li, B. Zhang, H. Qian, X.-D. Huan, W. Guan, W.-J. Xiao, J.-R. Chen, J. Am. Chem. Soc., 2021, 143, 13382-13392.
[16]	T. Guan, J.-Y. Guo, Q.-H. Zhang, X.-W. Xu, X.-Y. Yu, Y. Zhang, K. Zhao, Green Chem., 2022, 24, 6524-6530.
[17]	P.-Z. Wang, Y.-J. Liang, X. Wu, W. Guan, W.-J. Xiao, J.-R. Chen, ACS Catal., 2022, 12, 10925-10937.
[18]	R. Qi, Q. Chen, L. Liu, Z. Ma, D. Pan, H. Wang, Z. Li, C. Wang, Z. Xu, Nat. Commun., 2023, 14, 3295.
[19]	H.-C. Li, G.-N. Li, H.-S. Wang, Y. Tan, X.-L. Chen, B. Yu, Org. Chem. Front., 2023, 11, 135-141.
[20]	X.-J. Xu, Z.-M. Chi, R. Rui, Z. Zhang, H.-Z. Li, X.-Y. Liu, Adv. Synth. Catal., 2024, 366, 2607-2612.
[21]	J.-C. Hou, W. Cai, H.-T. Ji, L.-J. Ou, W.-M. He, Chin. Chem. Lett., 2025, 36, 110469.
[22]	P.-Z. Wang, W.-J. Xiao, J.-R. Chen, Chin. J. Catal., 2022, 43, 548-557.
[23]	T. Liu, C. Wang, Green Synth. Catal., 2025, https://doi.org/10.1016/j.gresc.2025.04.011.
[24]	H. Li, Y. Li, W. Yuan, A. Qu, K. Chen, Y. Zhu, Green Synth. Catal., 2024, 5, 159-164.
[25]	Y. Sumida, H. Ohmiya, Chem. Soc. Rev., 2021, 50, 6320-6332.
[26]	L. van Dalsen, R. E. Brown, J. A. Rossi-Ashton, D. J. Procter, Angew. Chem. Int. Ed., 2023, 62, e202303104.
[27]	B. Saxena, R. I. Patel, A. Sharma, Adv. Synth. Catal., 2023, 365, 1538-1564.
[28]	H. Xu, X. Li, Y. Dong, S. Ji, J. Zuo, J. Lv, D. Yang, Org. Lett., 2023, 25, 3784-3789.
[29]	X.-X. Zhang, H. Zheng, Y.-K. Mei, Y. Liu, Y.-Y. Liu, D.-W. Ji, B. Wan, Q.-A. Chen, Chem. Sci., 2023, 14, 11170-11179.
[30]	T. Yan, J. Yang, K. Yan, Z. Wang, B. Li, J. Wen, Angew. Chem. Int. Ed., 2024, 63, e202405186.
[31]	K. Sachidanandan, C. Stenftenagel, A. M. Cluff, G. A. McAlary, A. Joshy, B. Niu, S. Laulhé Org. Lett., 2025, 27, 5619-5624.
[32]	H. Zhao, V. D. Cuomo, J. A. Rossi-Ashton, D. J. Procter, Chem, 2024, 10, 1240-1251.
[33]	T. Xue, C. Ma, L. Liu, C. Xiao, S.-F. Ni, R. Zeng, Nat. Commun., 2024, 15, 1455.
[34]	X.-W. Gu, Y. Zhang, F. Zhao, H.-J. Ai, X.-F. Wu, Chin. J. Catal., 2023, 48, 214-223.
[35]	J. Gao, Z.-P. Ye, Y.-F. Liu, X.-C. He, J.-P. Guan, F. Liu, K. Chen, H.-Y. Xiang, X.-Q. Chen, H. Yang, Org. Lett., 2022, 24, 4640-4644.
[36]	T. Tasnim, M. J. Ayodele, S. P. Pitre, J. Org. Chem., 2022, 87, 10555-10563.
[37]	T. Tasnim, C. Ryan, M. L. Christensen, C. J. Fennell, S. P. Pitre, Org. Lett., 2022, 24, 446-450.
[38]	I. Bosque, T. Bach, ACS Catal., 2019, 9, 9103-9109.
[39]	M.-C. Fu, R. Shang, B. Zhao, B. Wang, Y. Fu, Science, 2019, 363, 1429-1434.
[40]	E. J. McClain, T. M. Monos, M. Mori, J. W. Beatty, C. R. J. Stephenson, ACS Catal., 2020, 10, 12636-12641.
[41]	E. de Pedro Beato, D. Spinnato, W. Zhou, P. Melchiorre, J. Am. Chem. Soc., 2021, 143, 12304-12314.
[42]	W. Zhou, S. Wu, P. Melchiorre, J. Am. Chem. Soc., 2022, 144, 8914-8919.
[43]	J. X. Wang, M. C. Fu, L. Y. Yan, X. Lu, Y. Fu, Adv. Sci., 2024, 11, 2307241.
[44]	M. Liang, J. Chen, Chem. Soc. Rev., 2013, 42, 3453-3488.
[45]	P. Blanchard, C. Malacrida, C. Cabanetos, J. Roncali, S. Ludwigs, Polym. Int., 2019, 68, 589-606.
[46]	C. Dai, L. Zhong, X. Gong, L. Zeng, C. Xue, S. Li, B. Liu, Green Chem., 2019, 21, 6606-6610.
[47]	T. A. Schaub, T. Mekelburg, P. O. Dral, M. Miehlich, F. Hampel, K. Meyer, M. Kivala, Chem. Eur. J., 2020, 26, 3264-3269.
[48]	A. Dewanji, L. van Dalsen, J. A. Rossi-Ashton, E. Gasson, G. E. M. Crisenza, D. J. Procter, Nat. Chem., 2023, 15, 43-52.
[49]	H.-Y. Wu, X. Tang, R. Guo, H. T. Ang, J. Nie, J. Wu, J.-A. Ma, F.-G. Zhang, Cell Rep. Phys. Sci., 2024, 5, 102135.
[50]	M.-Y. He, X. Tang, H.-Y. Wu, J. Nie, J.-A. Ma, F.-G. Zhang, Org. Lett., 2023, 25, 9041-9046.
[51]	S. Ji, X. Li, Y. Wang, D. Zhang, J. Lv, Y. Shi, D. Yang, Org. Lett., 2025, 27, 7892-7897.
[52]	H.-Y. Wu, X. Tang, R. Guo, F.-G. Zhang, J.-A. Ma, Chin. J. Chem., 2025, 43, 2642-2468
[53]	D. J. Castillo-Pazos, J. D. Lasso, E. Hamzehpoor, J. Ramos-Sánchez, J. M. Salgado, G. Cosa, D. F. Perepichka, C.-J. Li, Chem. Sci., 2023, 14, 3470-3481.
[54]	J. D. Lasso, D. J. Castillo-Pazos, J. M. Salgado, C. Ruchlin, L. Lefebvre, D. Farajat, D. F. Perepichka, C.-J. Li, J. Am. Chem. Soc., 2024, 146, 2583-2592.
[55]	H.-M. Huang, J. J. W. McDouall, D. J. Procter, Nat. Catal., 2019, 2, 211-218.
[56]	S. Jin, X. Sui, G. C. Haug, V. D. Nguyen, H. T. Dang, H. D. Arman, O. V. Larionov, ACS Catal., 2022, 12, 285-294.
[57]	W. Qiu, R. Tao, Y. He, Y. Zhou, K. Yang, Q. Song, Nat. Commun., 2024, 15, 10432.
[58]	X. Dang, Z. Li, J. Shang, C. Zhang, C. Wang, Z. Xu, Angew. Chem. Int. Ed., 2024, 63, e202400494.
[59]	C. Zhu, Q. Liu, N. Wang, R. Ma, K. Chen, P. J. Walsh, K. Guo, C. Feng, Angew. Chem. Int. Ed., 2025, 64, e202509664.
[60]	B.-Z. Chen, D.-W. Ji, B.-C. Zhou, X.-Y. Wang, H. Liu, B. Wan, X.-P. Hu, Q.-A. Chen, Chin. J. Catal., 2024, 59, 250-259.
[61]	G. Litwinienko, A. L. J. Beckwith, K. U. Ingold, Chem. Soc. Rev., 2011, 40, 2157-2163.
[62]	P.-J. Xia, Y.-Z. Hu, Z.-P. Ye, X.-J. Li, H.-Y. Xiang, H. Yang, J. Org. Chem., 2020, 85, 3538-3547.
[63]	X.-S. Hu, J.-X. He, S.-Z. Dong, Q.-H. Zhao, J.-S. Yu, J. Zhou, Nat. Commun., 2020, 11, 5500.
[64]	J.-C. Hou, H.-T. Ji, Y.-H. Lu, J.-S. Wang, Y.-D. Xu, Y.-Y. Zeng, W.-M. He, Chin. Chem. Lett., 2024, 35, 109514.

基于催化量电子供体-受体复合物自由基接力选择性地实现烯烃氰烷基双官能化

Photocatalyst-free chemoselective radical-relay strategy enabled cyanoalkyl difunctionalization of alkenes via catalytic EDA complex

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