Controlled Generation and Transformations of Alkene Radical Anions

doi:10.6023/cjoc202603031

Abstract

Alkene radical anions are a highly reactive class of intermediates that exhibit the dual reactivity of both radicals and carbanions, and thus hold unique value in organic synthesis. However, the controlled generation and highly selective transformation of these species remain challenging, mainly due to the dearth of efficient methods for their controlled generation, especially in catalytic manner. This resulted in many issues such as difficult stereocontrol, limited substrate scope, and the relatively narrow range of reaction patterns available. In recent years, with the continuous development and advancement of novel catalytic systems, the reaction types of alkene radical anions have been initially expanded, offering more possibilities for synthetic research in related fields. This review briefly summarizes three major strategies for the generation of alkene radical anions—chemical reduction, electrochemical reduction, and photochemical reduction—and discusses their applications in several important alkene transformation reactions from the perspectives of both generation modes and downstream reactivity. Finally, the future development of this field is also discussed.

Key words: alkene functionalization, alkene radical anion, single-electron reduction, radical reaction, visible light photocatalysis

Cite this article

Bin Zhang, Wenjing Xiao, Jiarong Chen. Controlled Generation and Transformations of Alkene Radical Anions[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1181-1204.

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Fig. & Tab. 48

Scheme 1. Reactivity of radical ion intermediates

Scheme 2. Overview of the generation and transformations of alkene radical ions

Scheme 3. Alkali-metal-promoted reduction and reductive dimerization of alkenes

Scheme 4. Na-mediated dimeric carboxylation of alkene radical anions

Scheme 5. Alkali metal-mediated disilylation of alkene radical anions

Scheme 6. DTBB-catalyzed dilithiation of styrene

Scheme 7. Regioselective Mg-promoted hydroacylation of alkenes

Scheme 8. Solvent-controlled reductive coupling of activated vinyl triflates with chlorotrimethylsilane by Mg

Scheme 9. Reductive difunctionalization of aryl alkenes with Na

Scheme 10. Iron mediated Z→E isomerization of alkenes

Scheme 11. Selective reduction of conjugated olefins mediated by SmI2

Scheme 12. Electrochemical reduction of 1,1-diaryl-substituted ethenes

Scheme 13. Electrochemical hydrogenation with gaseous ammonia

Scheme 14. Electrochemical reductive deuteration of electron-deficient alkenes

Scheme 15. Electrochemical reductive deuteration of aryl-substituted alkenes

Scheme 16. Electrochemical reductive acylation of electron deficient olefins

Scheme 17. Electrochemical acylation of aryl olefins

Scheme 18. Electroinduced reductive and dearomative alkene-aldehyde coupling

Scheme 19. Electrocatalytic hydrocarboxylation of aryl olefin radical anions

Scheme 20. Electrocatalytic hydrocarboxylation of 1,3-diene and electron deficient olefins

Scheme 21. Electrochemical lactamization with CO2

Scheme 22. Electrochemical defluorinative carboxylation of gem-difluoroalkenes with carbon dioxide

Scheme 23. Electrochemical intra- and intermolecular reductive dimerization of alkenes

Scheme 24. Intramolecular cycloaddition reaction of radical anions

Scheme 25. Proposed mechanism for anion radical cycloadditions

Scheme 26. Strongly reducing photosensitizers for the single-electron reduction of alkenes

Scheme 27. Hg lamp-promoted hydroalkoxylation / hydrocyanation of alkene radical anions

Scheme 28. Photocatalytic allylation of electron-deficient alkenes with allylsilanes

Scheme 29. Photoenzymatic hydrogenation of heteroaromatic olefins

Scheme 30. Reductive activation and hydrofunctionalization of olefins by multiphoton tandem photoredox catalysis

Scheme 31. Mechanism of olefin reductive activation via multiphoton tandem photoredox catalysis

Scheme 32. Visible-light-driven reductive hydrogenation of electron-deficient alkenes

Scheme 33. Photocatalytic reductive hydrogenation of electron-deficient alkenes/heteroarenes

Scheme 34. Photocatalytic nucleophilic addition of alcohols to alkenes

Scheme 35. Photocatalytic α-nucleophilic addition to α,β-un- saturated amides

Scheme 36. Photocatalytic Markovnikov hydroamination of alkenes with azoles

Scheme 37. Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis

Scheme 38. Photocatalytic reductive coupling of alkenes with ketones

Scheme 39. Photocatalytic reductive coupling of alkenes with aldehydes/isocyanate/amines/CO2

Scheme 40. Reductive cross-coupling of olefins via a radical anion pathway

Scheme 41. Trifluoromethylation and monofluoroalkenylation of alkenes through radical-radical cross-coupling

Scheme 42. EDA complex-enabled carbo-carboxylation of alkenes with CO₂

Scheme 43. Sequential radical-anionic polymerizations via consecutive photo-reduction

Scheme 44. Photocatalytic intra- and intermolecular [2＋2] cycloaddition of enones

Scheme 45. Intermolecular [2＋2] imine-olefin photocycloadditions enabled by Cu(I)

Scheme 46. Metallaphotoredox-catalyzed aminocarboxylation and alkynylcarboxylation of alkenes

Scheme 47. Enantioselective cyanofunctionalization of aromatic alkenes via radical anions

Scheme 48. Stereodivergent hydroalkoxylation of 1,3-dienes via dual photo and copper catalysis

References 59

[60]	Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102.
[61]	Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
[62]	Schultz, D. M.; Yoon, T. P. Science 2014, 343, 1239176.
[63]	Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075.
[64]	Twilton, J.; Le, C. ( C.); Zhang, P.; Shaw, M. H.; Evans, R. W.; MacMillan, D. W. C. Nat. Rev. Chem. 2017, 1, 0052.
[65]	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.
[1]	Weitz, E. Prog. Polym. Sci. 1928, 34, 538.
[2]	Roth, H. D. Tetrahedron 1986, 42, 6097.
[3]	McClelland, B. J. Chem. Rev. 1964, 64, 301.
[4]	Ischay, M. A.; Yoon, T. P. Eur. J. Org. Chem. 2012, 18, 3359.
[5]	Mendkovich, A. S.; Rusakov, A. I. Russ. J. Electrochem. 2023, 59, 999.
[6]	Wilger, D. J.; Grandjean, J.-M. M.; Lammert, T. R.; Nicewicz, D. A. Nat. Chem. 2014, 6, 720.
[7]	Margrey, K. A.; Nicewicz, D. A. Acc. Chem. Res. 2016, 49, 1997.
[8]	Qian, S.; Lazarus, T. M.; Nicewicz, D. A. J. Am. Chem. Soc. 2023, 145, 18247.
[66]	Li, X.; Tu, Y. L.; Chen, X. Y. Eur. J. Org. Chem. 2024, 27, e202301060.
[67]	Arnold, D. R.; Maroulis, A. J. J. Am. Chem. Soc. 1977, 99, 7355.
[68]	Mizuno, K.; Ikeda, M.; Otsuji, Y. Chem. Lett. 1988, 17, 1507.
[69]	Nakano, Y.; Black, M. I.; Meichan, A. J.; Braddock, A.; Sandoval, M. M.; Chung, M. M.; Biegasiewicz, K. F.; Zhu, T.; Hyster, T. K. Angew. Chem. Int. Ed. 2020, 59, 10484.
[70]	Czyz, M. L.; Taylor, M. S.; Horngren, T. H.; Polyzos, A. ACS Catal. 2021, 11, 5472.
[71]	Kang, W.-J.; Li, B.; Duan, M.; Pan, G.; Sun, W.; Ding, A.; Zhang, Y.; Houk, K. N.; Guo, H. Angew. Chem. Int. Ed. 2022, 61, e202211562.
[9]	Luo, M.-J.; Xiao, Q.; Li, J.-H. Chem. Soc. Rev. 2022, 51, 7206.
[10]	Franov, L. J.; Wilsdon, T. L.; Polyzos, A. Synlett. 2025, 36, 3269.
[11]	Xie, X.-Q.; Rao, C.-J.; Cheng, C.; Song, X.-R.; Luo, M.-J.; Xiao, Q. Q. Adv. Synth. Catal. 2026, 368, e70312.
[12]	Berthelot, M. Justus Liebigs Ann. Chem. 1867, 143, 97.
[13]	Schlenk, W.; Appenrodt, J.; Michael, A. Ber. Dtsch. Chem. Ges. 1914, 47, 473.
[14]	Wright, G. F. J. Am. Chem. Soc. 1939, 61, 2106.
[15]	Campbell, K. N.; Campbell, B. K. Chem. Rev. 1942, 31, 77.
[16]	Myers, G. S.; Richmond, H. H.; Wright, G. F. J. Am. Chem. Soc. 1947, 69, 710.
[72]	Brzezinski, C. U.; LeBlanc, A. R.; Clerici, M. G.; Wuest, W. M. Org. Lett. 2024, 26, 5534.
[73]	Penner, A.; Bätzner, E.; Wagenknecht, H. A. Synlett 2012, 23, 2803.
[74]	Speck, F.; Rombach, D.; Wagenknecht, H. A. Beilstein J. Org. Chem. 2019, 15, 52.
[75]	Seyfert, F.; Mitha, M.; Wagenknecht, H. A. Eur. J. Org. Chem. 2021, 9, 776.
[76]	Seyfert, F.; Wagenknecht, H. A. Synlett 2021, 32, 582.
[77]	Luan, Z. H.; Qu, J. P.; Kang, Y. B. J. Am. Chem. Soc. 2020, 142, 20942.
[78]	Nie, J.; Shi, Y.; Gan, M.; Huang, H.; Ji, X. Org. Lett. 2024, 26, 9481.
[17]	Reesor, J. W. B.; Smith, J. G.; Wright, G. F. J. Org. Chem. 1954, 19, 940.
[18]	Szwarc, M.; Levy, M.; Milkovich, R. J. Am. Chem. Soc. 1956, 78, 2656.
[19]	Szwarc, M. Makromol. Chem. 1960, 35, 132.
[20]	Frank, C. E.; Leebrick, J. R.; Moormeyer, L. F.; Scheben, J. A.; Homberg, O. J. Org. Chem. 1961, 26, 307.
[21]	Eisch, J. J.; Beuhler, R. J. J. Org. Chem. 1963, 28, 2876.
[22]	Eisch, J. J.; Gupta, G. J. Organomet. Chem. 1973, 50, C23.
[23]	Walker, J. F. US 2352461, 1944.
[24]	Frank, C. E.; Foster, W. E. J. Org. Chem. 1961, 26, 303.
[79]	Ju, T.; Zhou, Y.-Q.; Cao, K.-G.; Fu, Q.; Ye, J.-H.; Sun, G.-Q.; Liu, X.-F.; Chen, L.; Chen, L.; Liao, L.-L.; Yu, D.-G. Nat. Catal. 2021, 4, 304.
[80]	Venditto, N. J.; Liang, Y. S.; El Mokadem, R. K.; Nicewicz, D. A. J. Am. Chem. Soc. 2022, 144, 11888.
[81]	El Mokadem, R. K.; Lazarus, T. M.; Nicewicz, D. A. Chem 2025, 11, 102647.
[82]	Hu, D.; Dang, H.; Liang, Z.; Wang, D.; Du, Y.; Shen, C.; Shen, J.; Wang, M. Org. Lett. 2024, 26, 10797.
[83]	Czyz, M. L.; Horngren, T. H.; Kondopoulos, A. J.; Franov, L. J.; Forni, J. A.; Pham, L. N.; Coote, M. L.; Polyzos, A. Nat. Catal. 2024, 7, 1316.
[84]	Zhou, W.; Dmitriev, I. A.; Melchiorre, P. J. Am. Chem. Soc. 2023, 145, 25098.
[85]	Wang, Q.; Qu, Y.; Tian, H.; Liu, Y.; Song, H.; Wang, Q. Chem. Eur. J. 2019, 25, 8686.
[86]	Jiang, Y.-Y.; Chen, Z.; Jiang, Y.-X.; Zhu, W.-J.; Xu, J.-C.; Ye, J.-H.; Zhang, W.; Yu, D.-G. Chin. J. Chem. 2025, 43, 2341.
[87]	Eisch, J. J.; Gupta, G. J. Organomet. Chem. 1979, 168, 139.
[88]	Szwarc, M. Nature 1956, 178, 1168.
[89]	Zhao, H.; Liu, Y.; Ai, J.-X.; Nong, J.; Yue, J.-P.; Zheng, Y.; Zhu, J.-B.; Ye, J.-H.; Liao, S.; Pan, X.; Yu, D.-G. Angew. Chem. Int. Ed. 2026, 65, e202521319.
[25]	Frank, C. E.; Leebrick, J. R.; Moormeier, L. F.; Scheben, J. A.; Homberg, O. J. Org. Chem. 1961, 26, 307.
[26]	Weyenberg, D. R.; Toporcer, L. H.; Bey, A. E. J. Org. Chem. 1965, 30, 4096.
[27]	Kira, M.; Hino, T.; Kubota, Y.; Matsuyama, N.; Sakurai, H. Tetrahedron Lett. 1988, 29, 6939.
[28]	Yus, M.; Martinez, P.; Guijarro, D. Tetrahedron 2001, 57, 10119.
[29]	Ohno, T.; Sakai, M.; Ishino, Y.; Shibata, T.; Maekawa, H.; Nishiguchi, I. Org. Lett. 2001, 3, 3439.
[30]	Nishiguchi, I.; Yamamoto, Y.; Sakai, M.; Ohno, T.; Ishino, Y.; Maekawa, H. Synlett 2002, 5, 759.
[90]	Ischay, M. A.; Anzovino, M. E.; Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2008, 130, 12886.
[91]	Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2009, 131, 14604.
[92]	Flores, D. M.; Neville, M. L.; Schmidt, V. A. Nat. Commun. 2022, 13, 2764.
[93]	Lang, X.; Zhao, J.; Chen, X. Chem. Soc. Rev. 2016, 45, 3026.
[94]	Wang, P.-Z.; Zhang, B.; Xiao, W.-J.; Chen, J.-R. Acc. Chem. Res. 2024, 57, 3433.
[95]	Yue, J.-P.; Xu, J.-C.; Luo, H.-T.; Chen, X.-W.; Song, H.-X.; Deng, Y.; Yuan, L.; Ye, J.-H.; Yu, D.-G. Nat. Catal. 2023, 6, 959.
[96]	Xu, J.-C.; Yue, J.-P.; Pan, M.; Chen, Y.-C.; Wang, W.; Zhou, X.; Zhang, W.; Ye, J.-H.; Yu, D.-G. Nat. Commun. 2025, 16, 1850.
[31]	Maekawa, H.; Nishiyama, Y. Tetrahedron 2015, 71, 6694.
[32]	Maekawa, H.; Noda, K.; Kuramochi, K.; Zhang, T. Org. Lett. 2018, 20, 1953.
[33]	Fukazawa, M.; Takahashi, F.; Nogi, K.; Sasamori, T.; Yorimitsu, H. Org. Lett. 2020, 22, 2303.
[34]	Sorensen, S.; Levin, G.; Szwarc, M. J. Am. Chem. Soc. 1975, 97, 2341.
[35]	Abdul-Rahim, O.; Simonov, A. N.; Boas, J. F.; Rüther, T.; Collins, D. J.; Perlmutter, P.; Bond, A. M. J. Phys. Chem. B 2014, 118, 3183.
[36]	Sieg, G.; Müller, I.; Weißer, K.; Werncke, C. G. Chem. Sci. 2022, 13, 13872-13878.
[97]	Zhang, B.; Li, T.-T.; Mao, Z.-C.; Jiang, M.; Zhang, Z.; Zhao, K.; Qu, W.-Y.; Xiao, W.-J.; Chen, J.-R. J. Am. Chem. Soc. 2024, 146, 1410.
[98]	Jin, Y.; Li, Y.; Tang, J.; Wang, Z.; Chen, J.; Zhang, Z.; Cheng, B. Org. Lett. 2025, 27, 10000.
[99]	Yang, G.; Wang, Y.; Qiu, Y. Chin. J. Org. Chem. 2021, 41, 3935.
[100]	Wu, S.; Kaur, J.; Karl, T. A.; Tian, X.; Barham, J. P. Angew. Chem. Int. Ed. 2022, 61, e202107811.
[37]	Dahleń A.; Hilmersson, G. Tetrahedron Lett. 2003, 44, 2661.
[38]	Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230.
[39]	Wiebe, A.; Gieshoff, T.; Möhle, S.; Rodrigo, E.; Zirbes, M.; Wald- vogel, S. R. Angew. Chem. Int. Ed. 2018, 57, 5594.
[40]	Zhang, Y.; Zhou, Z.-L.; Li, J.-H.; Li, Y.-T. Chem. Rec. 2025, 25, e202400263.
[41]	Wang, C.-R.; Zhang, W.-Y.; Yu, C.; Li, Y.; Li, J.-H. Chin. J. Chem. 2025, 43, 3676.
[42]	Wawzonek, S.; Blaha, E. W.; Berkey, R.; Runner, M. E. J. Electrochem. Soc. 1955, 102, 235.
[43]	Wawzonek, S.; Wearing, D. J. Am. Chem. Soc. 1959, 81, 2067
[44]	Fruianu, M.; Marchetti, M.; Melloni, G.; Sanna, G.; Seeber, R. J. Chem. Soc., Perkin Trans. 2 1994, 2039.
[45]	Li, J.; He, L.; Liu, X.; Cheng, X.; Li, G.-G. Angew. Chem. Int. Ed. 2019, 58, 1759.
[46]	Bi, C.; Zhao, X.; Jia, Z.; Chang, Y.; Yang, H.; Song, M.; Zhang, X.; Zhang, Y.; Qing, G. ChemCatChem 2023, 15, e202300258.
[47]	Liu, X.; Liu, R.; Qiu, J.; Cheng, X.; Li, G. Angew. Chem. Int. Ed. 2020, 59, 13962.
[48]	Yang, K.; Feng, T.; Qiu, Y. Angew. Chem. Int. Ed. 2023, 62, e202312803.
[49]	Lund, H.; Degrand, C. Tetrahedron Lett. 1977, 18, 3593.
[50]	Shono, T.; Nishiguchi, I.; Ohmizu, H. J. Am. Chem. Soc. 1977, 99, 7396.
[51]	Engels, R.; Schäfer, H. J. Angew. Chem. Int. Ed. Engl. 1978, 17, 460.
[52]	Franov, L. J.; Wilsdon, T. L.; Czyz, M. L.; Polyzos, A. J. Am. Chem. Soc. 2024, 146, 29450.
[53]	Alkayal, A.; Tabas, V.; Montanaro, S.; Wright, I. A.; Malkov, A. V.; Buckley, B. R. J. Am. Chem. Soc. 2020, 142, 1780.
[54]	Sheta, A. M.; Mashaly, M. A.; Said, S. B.; Elmorsy, S. S.; Malkov, A. V.; Buckley, B. R. Chem. Sci. 2020, 11, 9109.
[55]	Sheta, A. M.; Alkayal, A.; Mashaly, M. A.; Said, S. B.; Elmorsy, S. S.; Malkov, A. V.; Buckley, B. R. Angew. Chem. Int. Ed. 2021, 60, 21832.
[56]	Zhang, R.; Liu, M.; Zhao, Z.; Qiu, Y. Green Chem. 2025, 27, 1658.
[57]	Xie, S.-L.; Gao, X.-T.; Wu, H.-H.; Zhou, F.; Zhou, J. Org. Lett. 2020, 22, 8424.
[58]	Zhang, W.; Zhang, S.; Fan, W.-J.; Chen, S.; Xiong, M.; Chen, L. Green Chem. 2025, 27, 11222.
[59]	Yang, J.; Felton, G. A. N.; Bauld, N. L.; Krische, M. J. Am. Chem. Soc. 2004, 126, 1634.

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