光氧化还原催化炔烃的双碳官能团化反应进展

doi:10.6023/cjoc202512019

摘要/Abstract

光氧化还原催化炔烃的双碳官能团化反应是有机合成领域的前沿研究方向之一. 该策略通过单电子转移、能量转移或质子耦合电子转移等机制活化底物, 实现炔烃的高效、高选择性双碳官能团化. 与传统方法相比, 可见光催化策略具有条件温和、底物适用范围广、官能团兼容性和反应选择性好等优势, 为多取代烯烃、环状骨架及生物活性分子的高效合成提供了新范式. 系统综述了可见光催化炔烃双碳官能团化的最新研究进展, 重点阐述了底物适用范围、反应机理、选择性调控策略以及合成应用, 并对未来发展趋势进行了展望.

关键词: 光氧化还原催化, 过渡金属催化, 炔烃, 区域选择性, 双碳官能团化

Photoredox-catalyzed dicarbofunctionalization of alkynes has emerged as a cutting-edge research direction in organic synthesis. This strategy ingeniously integrates the mild activation capabilities of photochemistry with the efficient bond-forming characteristics of transition metal catalysis. Through mechanisms such as single-electron transfer, energy transfer, or proton-coupled electron transfer, highly selective dicarbofunctionalization of alkynes can be achieved under visible light conditions. Compared with traditional methods, this approach not only offers mild reaction conditions and excellent functional group tolerance, but also enables precise control over chemo-, regio-, and stereoselectivity, thereby providing a new paradigm for the efficient synthesis of polysubstituted alkenes, cyclic compounds, and bioactive molecules. This review systematically summarizes the latest advances in this field with a focus on the substrate scope, reaction mechanisms, strategies for selectivity control, and synthetic applications, while also offering perspectives on future development trends.

Key words: photoredox catalysis, transition metal catalysis, alkynes, regioselectivity, dicarbofunctionalization

引用此文

叶富, 袁伟明. 光氧化还原催化炔烃的双碳官能团化反应进展[J]. 有机化学, 2026, 46(4): 1146-1165.

Fu Ye, Weiming Yuan. Recent Advances in Dicarbofunctionalization of Alkynes via Photoredox Catalysis[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1146-1165.

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

分享此文

图/表 25

图式1. 光氧化还原催化炔烃的双碳官能团化反应

Scheme 1. Dicarbofunctionalization of alkynes via photoredox catalysis

图式2. 光氧化还原催化酮酸和炔烃的双碳官能团化反应

Scheme 2. Dicarbofunctionalization of ketone acids and alkynes via photoredox catalysis

图式3. 光氧化还原催化酮酸和乙炔的双碳官能团化反应

Scheme 3. Dicarbofunctionalization of ketone acids and acetylene via photoredox catalysis

图式4. 光氧化还原催化自由基加成/环化构筑苯并6,5-螺缩酮糖苷

Scheme 4. Synthesis of 6,5-benzospiroketal glycosides via photoredox-catalyzed radical addition/cyclization

图式5. 光氧化还原催化炔烃的双氰基化反应

Scheme 5. Photoredox-catalyzed dicyanation of alkynes

图式6. 光氧化还原催化氢原子转移介导的醛与炔[3＋2]环加成反应构建环戊酮

Scheme 6. Photoredox-catalyzed hydrogen atom transfer-enabled [3＋2] cycloaddition of aldehydes and alkynes for the synthesis of cyclopentanones

图式7. 光氧化还原催化未活化炔烃与CO2的1,2-双羧基化反应

Scheme 7. Photoredox-catalyzed 1,2-dicarboxylation of unactivated alkynes with CO2

图式8. 基于自由基加成/迁移策略的光催化远程C(sp3)—H键烯基化反应

Scheme 8. Photoredox-catalyzed remote C(sp3)—H vinylation via a radical addition/translocation strategy

图式9. 光氧化还原催化乙烯基自由基介导的炔烃与烯烃/芳烃远程碳胺化反应

Scheme 9. Photoredox-catalyzed remote carboamination via vinyl radicals generated from alkynes with olefins/arenes

图式10. 光氧化还原催化非活化炔烃的双碳官能团化反应

Scheme 10. Dicarbofunctionalization of unactivated alkynes via photoredox catalysis

图式11. 光氧化还原催化非活化炔烃的双碳官能团化反应机理

Scheme 11. Mechanism of dicarbofunctionalization of unactivated alkynes via photoredox catalysis

图式12. 光氧化还原催化炔烃的吡啶氰基化反应

Scheme 12. Alkyne pyridylcyanation via photoredox catalysis

图式13. 光氧化还原催化炔烃的吡啶氰基化反应机理

Scheme 13. Mechanism of alkyne pyridylcyanation via photoredox catalysis

图式14. 光/镍协同催化炔烃顺式选择性芳基烷基化反应

Scheme 14. Photoredox/nickel dual catalysis for cis-selective arylalkylation of alkynes

图式15. 光/镍协同催化炔烃顺式选择性芳基烷基化反应机理

Scheme 15. Mechanism of photoredox/nickel dual catalysis for cis-selective arylalkylation of alkynes

图式16. 光/镍协同催化炔烃的1,2-碳烯丙基化反应

Scheme 16. Photoredox/nickel dual catalysis for 1,2-carboallylation of alkynes

图式17. 光/镍协同催化炔烃的1,2-碳烯丙基化反应机理

Scheme 17. Mechanism of photoredox/nickel dual catalysis for 1,2-carboallylation of alkynes

图式18. 光/镍协同催化炔烃的酰基烷基化反应

Scheme 18. Photoredox/nickel dual catalysis for acyl-alkylation of Alkynes

图式19. 光/镍协同催化炔烃的分子间1,2-碳氰化反应

Scheme 19. Photoredox/nickel dual catalysis for intermolecular 1,2-carbocyanation of alkynes

图式20. 光/镍协同催化炔烃的芳基烷基化反应

Scheme 20. Photoredox/nickel dual catalysis for arylalkylation of alkynes

图式21. 光/镍协同催化炔烃的芳基烷基化反应机理

Scheme 21. Mechanism of photoredox/nickel dual catalysis for arylalkylation of alkynes

图式22. 电/光/镍协同催化烯烃的立体发散合成反应

Scheme 22. Electrochemical/photochemical/nickel dual catalysis for stereodivergent synthesis of alkenes

图式23. 光/镍协同催化乙炔的芳基烷基化反应

Scheme 23. Photoredox/nickel dual catalysis for arylalkylation of acetylene

图式24. 光/铜协同催化末端炔烃的反式选择性双碳官能化反应

Scheme 24. Photoredox/copper-cocatalyzed anti-selective dicarbofunctionalization of terminal alkynes

图式25. 光/钴协同催化炔烃的选择性双碳官能化反应

Scheme 25. Photoredox/cobalt-cocatalyzed selective dicarbofunctionalization of alkynes

参考文献 40

[1]	(a) Yu, X.; Zhu, S. F. Chem. Soc. Rev. 2025, 54, 5586.
	(b) Chen, L.; Chen, K.; Zhu, S. Chem 2018, 4, 1208.
	(c) Patel, M.; Saunthwal, R. K.; Verma, A. K. Acc. Chem. Res. 2017, 50, 240.
	(d) Alabugin, I. V.; Gonzalez-Rodriguez, E. Acc. Chem. Res. 2018, 51, 1206.
	(e) Worch, J. C.; Stubbs, C. J.; Price, M. J.; Dove, A. P. Chem. Rev. 2021, 121, 6744.
[2]	(a) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285.
	(b) Negishi, E.; Huang, Z.; Wang, G.; Mohan, S.; Wang, C.; Hattori, H. Acc. Chem. Res. 2008, 41, 1474.
	(c) Dorel, R.; Echavarren, A. M. Chem. Rev. 2015, 115, 9028.
[3]	(a) Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102.
	(b) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
	(c) Chen, J.-R.; Hu, X.-Q.; Lu, L.-Q.; Xiao, W.-J. Chem. Soc. Rev. 2016, 45, 2044.
[4]	(a) Li, K.; Long, X.; Huang, Y.; Zhu, S. Acta Chim. Sinica 2024, 82, 658 (in Chinese).
	(李康葵, 龙先扬, 黄岳, 祝诗发, 化学学报, 2024, 82, 658.)
	(b) Zhu, S.; Zhao, X.; Li, H.; Chu, L. Chem. Soc. Rev. 2021, 50, 10836.
[5]	(a) Chan, A. Y.; Perry, I. B.; Bissonnette, N. B.; Buksh, B. F.; Edwards, G. A.; Frye, L. I.; Garry, O. L.; Lavagnino, M. N.; Li, B. X.; Liang, Y.; Mao, E.; Millet, A.; Oakley, J. V.; Reed, N. L.; Sakai, H. A.; Seath, C. P.; MacMillan, D. W. C. Chem. Rev. 2022, 122, 1485.
	(b) Chang, L.; An, Q.; Duan, L.; Feng, K.; Zuo, Z. Chem. Rev. 2022, 122, 2429.
	(c) Lü S.; Xie, J. ACS Catal. 2025, 15, 7749.
	(d) Xie, J.; Jin, H.; Hashmi, A. S. K. Chem. Soc. Rev. 2017, 46, 5193.
[6]	(a) Zhu, C.; Yue, H.; Chu, L.; Rueping, M. Chem. Sci. 2020, 11, 4051.
	(b) Gupta, S.; Kundu, A.; Ghosh, S.; Chakraborty, A.; Hajra, A. Green Chem. 2023, 25, 8459.
	(c) Xu, L.; Wang, F.; Chen, F.; Zhu, S.; Chu, L. Chin. J. Org. Chem. 2022, 42, 1 (in Chinese).
	(徐磊, 王方, 陈凡, 朱圣卿, 储玲玲, 有机化学, 2022, 42, 1.)
[7]	(a) Wang, Y.; Bao, Z.-P.; Mao, X.-D.; Hou, M.; Wu, X.-F. Chem. Soc. Rev. 2025, 54, 9530.
	(b) Qi, X.; Diao, T. ACS Catal. 2020, 10, 8542.
	(c) Ping, Y.; Song, H.; Kong, W. Chin. J. Org. Chem. 2022, 42, 3302 (in Chinese).
	(平媛媛, 宋海霞, 孔望清, 有机化学, 2022, 42, 3302.)
	(d) Luo, Y.; Zhang, X. Chin. J. Chem. 2024, 42, 3499.
	(e) Dhungana, R. K.; KC, S.; Basnet, P.; Giri, R. Chem. Rec. 2018, 18, 1314.
	(f) Gao, P.; Niu, Y.-J.; Yang, F.; Guo, L.-N.; Duan, X.-H. Chem. Commun. 2022, 58, 730.
	(g) Dong, Z.; Song, L.; Chen, L.-A. ChemCatChem 2023, 15, e202300803.
[8]	Guo, B.; Pu, Y.; Wang, S.; Gou, F.; Ju, H.; Chen, X.; Liu, Z.; Feng, Z. Chem. Commun. 2025, 61, 10668.
[9]	(a) Chen, Z.; Rong, M.-Y.; Nie, J.; Zhu, X.-F.; Shi, B.-F.; Ma, J.-A. Chem. Soc. Rev. 2019, 48, 4921.
	(b) Choi, J.; Fu, G. C. Science 2017, 356, eaaf7230.
	(c) Geist, E.; Kirschning, A.; Schmidt, T. Nat. Prod. Rep. 2014, 31, 441.
	(d) Zeng, X. Chem. Rev. 2013, 113, 6864.
[10]	(a) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079.
	(b) Severin, R.; Doye, S. Chem. Soc. Rev. 2007, 36, 1407.
	(c) Wen, H.; Liu, G.; Huang, Z. Coord. Chem. Rev. 2019, 386, 138.
	(d) Lu, H.; Yu, T.-Y.; Xu, P.-F.; Wei, H. Chem. Rev. 2021, 121, 365.
[11]	Yang, B.; Li, S.-J.; Wang, Y.; Lan, Y.; Zhu, S. Nat. Commun. 2021, 12, 5257.
[12]	Yang, B.; Lu, S.; Wang, Y.; Zhu, S. Nat. Commun. 2022, 13, 1858.
[13]	(a) Maddirala, A. R.; Tamadonfar, K.; Pinkner, J. S.; Sanick, D.; Hultgren, S. J.; Janetka, J. W. J. Med. Chem. 2024, 67, 3668.
	(b) Poletti, L.; Massi, A.; Ragno, D.; Droghetti, F.; Natali, M.; De Risi, C.; Bortolini, O.; Carmine, G. Org. Lett. 2023, 25, 4862.
[14]	Li, C.; Yu, S. Org. Lett. 2025, 27, 1281.
[15]	Zhang, Y.; Han, Y.; Zhu, S.; Qing, F.-L.; Xue, X.-S.; Chu, L. Angew. Chem. Int. Ed. 2022, 61, e202210838.
[16]	Le, S.; Li, J.; Feng, J.; Zhang, Z.; Bai, Y.; Yuan, Z.; Zhu, G. Nat. Commun. 2022, 13, 4734.
[17]	(a) Sekine, K.; Yamada, T. Chem. Soc. Rev. 2016, 45, 4524.
	(b) Grignard, B.; Gennen, S.; Jérôme, C.; Kleij, A. W.; Detrembleur, C. Chem. Soc. Rev. 2019, 48, 4466.
[18]	Wang, W.; Yan, S.-S.; Liu, Y.; Zhu, J.-S.; Yang, J.-W.; Xu, J.-C.; Tao, Y.-Y.; Li, J.-C.; Song, L.; Ye, J.-H.; Yu, D.-G. J. Am. Chem. Soc. 2025, 147, 23715.
[19]	(a) Chen, F.; Cao, Z.; Zhu, C. Chem. Commun. 2024, 60, 14912.
	(b) Cao, Z.; Zhu, C. Nat. Chem. 2024, 16, 1576.
	(c) Ma, Z.; Wu, X.; Zhu, C. Chem. Rec. 2023, 23, e202200221.
	(d) Wei, Y.; Wu, X.; Zhu, C. Synlett 2022, 33, 1017.
	(e) Yue, B.; Wu, X.; Zhu, C. Chin. J. Org. Chem. 2022, 42, 458 (in Chinese).
	(乐柏佟, 吴新鑫, 朱晨, 有机化学, 2022, 42, 458.)
	(f) Wu, X.; Ma, Z.; Feng, T.; Zhu, C. Chem. Soc. Rev. 2021, 50, 11577.
	(g) Wu, X.; Zhu, C. Acc Chem. Res. 2020, 53, 1620.
	(h) Wu, X.; Zhu, C. CCS Chem. 2020, 2, 813.
[20]	Wu, S.; Wu, X.; Wang, D.; Zhu, C. Angew. Chem. Int. Ed. 2019, 58, 1499.
[21]	Wang, X.; Wang, J.; Ji, M.; Wu, X.; Zhu, C. Chem. Commun. 2024, 60, 4894.
[22]	Li, S.-S.; Jiang, Y.-S.; Luo, X.-L.; Ran, X.; Li, Y.; Wu, D.; Pan, C.-X.; Xia, P.-J. Sci. China Chem. 2024, 64, 558.
[23]	Luo, X.-L.; Huang, M.-S.; Li, S.-S.; Jiang, Y.-S.; Chen, L.-N.; Li, S.-H.; Xia, P.-J. Org. Lett. 2023, 25, 6407.
[24]	Li, S.-S.; Yang, H.-Y.; Ye, Z.-P.; Luo, J.; Chen, D.-N.; Chen, L.-N.; Pan, C.-X.; Xia, P.-J. Org. Lett. 2025, 27, 10129.
[25]	(a) Wille, U. Chem. Rev. 2013, 113, 813.
	(b) Chu, J. C. K.; Rovis, T. Nature 2016, 539, 272.
	(c) Sarkar, S.; Cheung, K. P. S.; Gevorgyan, V. Chem. Sci. 2020, 11, 12974.
[26]	Wang, J.; Wu, X.; Cao, Z.; Zhang, X.; Wang, X.; Li, J.; Zhu, C. Adv. Sci. 2024, 11, 2309022.
[27]	Tong, X.; Jie, J.; Liu, Y.; Yu, H.; Yuan, M.; Ang, H. T.; Wang, G.; Tian, D.; Su, H.; Wu, J. Nat. Commun. 2025, 16, 8985.
[28]	(a) Levin, M. D.; Kim, S.; Toste, F. D. ACS Cent. Sci. 2016, 2, 293.
	(b) Skubi, K. L.; Blum, T. R.; Yoon, T. P. Chem. Rev. 2016, 116, 10035.
	(c) Hossain, A.; Bhattacharyya, A.; Reiser, O. Science 2019, 364, 450.
[29]	Guo, L.; Song, F.; Zhu, S.; Li, H.; Chu, L. Nat. Commun. 2018, 9, 4543.
[30]	Qin, J.; Zhang, Z.; Lu, Y.; Zhu, S.; Chu, L. Chem. Sci. 2023, 14, 12143.
[31]	Pan, X.-H.; Shi, C.-X.; Hou, Y.-P.; Wang, L.-F.; Niu, R.-Q.; Guo, L. Org. Lett. 2024, 26, 9498.
[32]	(a) Tennent, C. L.; Jones, W. D. Can. J. Chem. 2005, 83, 626.
	(b) Quirós, I.; Martín, M.; Gomez-Mendoza, M.; Cabrera-Afonso, M. J.; Liras, M.; Fernández, I.; Nóvoa, L.; Tortosa, M. Angew. Chem. Int. Ed. 2024, 63, e202317683.
[33]	Qin, J.; Li, Y.; Hu, Y.; Huang, Z.; Miao, W.; Chu, L. J. Am. Chem. Soc. 2024, 146, 27583.
[34]	Raviola, C.; Protti, S.; Ravelli, D.; Fagnoni, M. Green Chem. 2019, 21, 748.
[35]	(a) Capaldo, L.; Ravelli, D.; Fagnoni, M. Chem. Rev. 2022, 122, 1875.
	(b) Shaw, M. H.; Twilton, J.; MacMillan, D. W. C. J. Org. Chem. 2016, 81, 6898.
[36]	Yue, H.; Zhu, C.; Kancherla, R.; Liu, F.; Rueping, M. Angew. Chem. Int. Ed. 2020, 59, 5738.
[37]	Zhu, C.; Yue, H.; Rueping, M. Nat. Commun. 2022, 13, 3240.
[38]	Li, K.; Long, X.; Zhu, S. ACS Catal. 2023, 13, 2422.
[39]	Tang, F.; Feng, Y.-S.; Cheng, Z.-F.; Zhang, Q.; Xu, H.-J. Org. Lett. 2023, 25, 3916.
[40]	Xiong, W.; Zhao, R.-R.; Wang, H.-S.; Lu, L.-Q.; Gao, K.; Xiao, W.-J. CCS Chem. 2025, 7, 3616.