钯催化下α-溴代腈与末端烯烃的Heck型偶联反应

doi:10.6023/cjoc202603018

研究论文

钯催化下α-溴代腈与末端烯烃的Heck型偶联反应

班银^a, 杨建^a, 杨莎莎^a, 满雪玉^b,*, 黄洋^a,*

^a遵义医科大学药学院贵州省化学药物创制全省重点实验室贵州遵义 563003;
^b湖南医药学院药学院湖南怀化 418000

收稿日期:2026-06-12 修回日期:2026-06-30
基金资助:
遵义医科大学 (No. F-1119)资助项目.

Palladium-Catalyzed Heck-Type Reaction of α-Bromonitriles with Terminal Alkenes

Ban Yin^a, Yang Jian^a, Yang Shasha^a, Man Xueyu^b,*, Huang Yang^a,*

^aGuizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals,School of Pharmacy, Zunyi Medical University, Zunyi, 563003;
^bSchool of Pharmaceutical Sciences, Hunan University of Medicine, Huaihua, Hunan, 418000

Received:2026-06-12 Revised:2026-06-30
Contact: *E-mail: yanghuang@zmu.edu.cn; xueyu_man@foxmail.com
Supported by:
Zunyi Medical University (No. F-1119).

文章分享

1. cjoc202603018辅助材料.pdf(5843KB)

摘要/Abstract

α-溴代腈是一类重要的合成砌块,被应用于合成含有氰基烷基结构的化合物中。然而,其在过渡金属钯催化下的偶联反应尚未有研究。该反应体系面临两个关键的问题：其一,α-溴代腈可能会与钯配位,从而影响催化效率;其次,该底物易发生β-氢消除副反应。针对上述挑战,本研究发展了α-溴代腈与末端烯烃在钯催化下的Heck偶联反应。该反应条件温和、操作简便,具有良好官能团兼容性和广泛的底物普适性。此外,该方法也适用于药物分子的后期官能团化修饰,展示出了良好的合成应用潜力。

关键词: α-溴代腈, 钯催化, 末端烯烃, Heck偶联反应

α-Bromonitriles represented an important synthetic building block. They have been used to prepare compounds containing cyanoalkyl groups. However, their coupling reactions under palladium catalysis remains unexplored. This reaction presents two challenges: firstly, α-bromonitriles may coordinate with palladium and lower its catalytic activity. Second, they tend to undergo β-hydrogen elimination. To solve these problems, we developed a palladium-catalyzed Heck coupling between α-bromonitriles and terminal alkenes. This operationally simple protocol proceeds under mild conditions, and exhibits broad functional group compatibility as well as a wide substrate scope. Furthermore, the method is applicable to the late-stage functionalization of pharmaceutical molecules, demonstrating its potential for synthetic applications.

Key words: α-bromonitriles, palladium-catalyzed, terminal alkenes, Heck-type reaction

引用此文

班银, 杨建, 杨莎莎, 满雪玉, 黄洋. 钯催化下α-溴代腈与末端烯烃的Heck型偶联反应[J]. 有机化学, doi: 10.6023/cjoc202603018.

Ban Yin, Yang Jian, Yang Shasha, Man Xueyu, Huang Yang. Palladium-Catalyzed Heck-Type Reaction of α-Bromonitriles with Terminal Alkenes[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202603018.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Fleming F. F.; Yao L.; Ravikumar P. C.; Funk L.; Shook, B. C. J. Med. Chem.2010, 53, 7902.
[2] Wang X.; Wang Y.; Li X.; Yu Z.; Song C.; Du, Y. RSC Med. Chem.2021, 12, 1650.
[3] Tiz D. B.; Mangiavacchi F.; Sancineto L.Phosphorus Sulfur Silicon Relat. Elem. 2026, DOI: 10.1080/10426507.2025.2611024.
[4] Chen S.; Wen K.; Fan J.; Bando Y.; Golberg, D. J. Mater. Chem. A.2018, 6, 11631.
[5] Hou J.; Yang M.; Wang D.; Zhang, J. Adv. Energy Mater.2020, 10, 1904252.
[6] Li N.; Ma J.; Huang T.; Shen Y.; Shen. M.; Jiang Y.; Hong T.; Ma G.; Ma, Z. Energy Stor. Sci. Tech.2025, 14, 997.
[7] (a) Hirpara, K. V.; Patel, S. P.; Parikh, K. A.; Bhimani, A. S.; Parekh, H. H. J. Sci., Islamic Repub. Iran 2004,15, 135.
(b) Guillemont, J.; Pasquier, E.; Palandjian, P.; Vernier, D.; Gaurrand, S.; Lewi, P. J.; Heeres, J.; de Jonge, M. R.; Koymans, L. M. H.; Daeyaert, F. F. D.; Vinkers, M. H.; Arnold, E.; Das, K.; Pauwels, R.; Andries, K.; de Béthune, M.-P.; Bettens, E.; Hertogs, K.; Wigerinck, P.; Timmerman, P.; Janssen, P. A. J. J. Med. Chem. 2004, 48, 2072.
[8] (a) Murakami, M.; Kato, T.; Mukaiyama, T. Chem. Lett. 1987, 1167.
(b) Kanai, T.; Kanagawa, Y.; Ishii, Y. J. Org. Chem. 1990, 55, 3274.
(c) Tsuji, Y.; Yamada, N.; Tanaka, S. J. Org. Chem. 1993, 58, 16.
(d) Yoneda, R.; Harusawa, S.; Kurihara, T. J. Org. Chem. 1991, 56, 1827.
(e) Tsuji, Y.; Kusui, T.; Kojima, T.; Sugiura, Y.; Yamada, N.; Tanaka, S.; Ebihara, M.; Kawamura, T. Organometallics 1998, 17, 4835.
(f) Soltani Rad, M. N.; Khalafi-Nezhad, A.; Behrouz, S.; Faghihi, M. A. Tetrahedron Lett. 2007, 48, 6779.
[9] Choi J.; Fu, G. C. J. Am. Chem. Soc.2012, 134, 9102.
[10] Yang Y.; Tang S.; Liu C.; Zhang H.; Sun Z.; Lei, A. Org. Bio. Chem.2011, 9, 5343.
[11] Shimkin K. W.; Gildner P. G.; Watson, D. A. Org. Lett.2016, 18, 988.
[12] Donslund A. S.; Neumann K. T.; Corneliussen N. P.; Grove E. K.; Herbstritt D.; Dagsbjerg K.; Skrydstrup, T. Chem. Eur. J.2019, 25, 14359.
[13] Tang S.; Liu C.; Lei A. Chem. Commun.2013, 49, 2442.
[14] Wen J.-L.; Guo P.; Pu G.-L.; Man X.-Y.; He, C.-Y. Chin. J. Org. Chem.2025, 45, 4405 (in Chinese).
(温吉林, 郭鹏, 蒲国良, 满雪玉, 贺春阳. 有机化学, 45, 4405.)
[15] Xie, J.; Han, J.; Liu, X.; Yue, H. Org, Lett. 2026, 28, 7, 2415.
[16] Yang J.; Zhang M.; Ban Y.; Hou Z.; Xiao X.; Yao Q.; Huang Y. Org. Lett.2026, 28, 2753.
[17] McMahon C.M.; Alexanian, E.J. Angew. Chem. Int. Ed.2014, 53, 5974.
[18] Shu L.; Dong X.; Sun Z.-H.; Zhao A.; Jiang M.; Ren X.; Yan F.; Cao K.; Liu Q.; Liu H. Org. Lett.2024, 26, 5719.
[19] Lee G.S.; Kim D.; Hong, S. H. Nat. Commun.2021, 12, 991.
[20] Liu Z.; Wei S.; Liang A.; Li J.; Zou, D. Wu Y.; Wu Y. Tetrahedron Lett.2019, 60, 485.
[21] Kurandina D.; Rivas M.; Radzhabov M.; Gevorgyan V. Org. Lett.2018, 20, 357.
[22] Jiang Y.; Liao Y.; Zhao Y.; Pan F. Org. Lett.2025, 27, 1344.
[23] Feng Z.; Min Q.-Q.; Zhao H.-Y.; Gu J.-W.; Zhang, X. Angew. Chem., Int. Ed.2015, 54, 1270.
[24] Feng Z.; Min Q.-Q.; Zhang X. Synthesis2015, 47, 2912.
[25] Feng Z.; Xiao Y.-L.; Zhang, X. Org. Chem. Front.2016, 3, 466.