手性有机硒化合物的合成研究进展

doi:10.6023/cjoc202509022

摘要/Abstract

手性有机硒化合物广泛存在于活性生物分子、天然产物、药物分子和功能材料等领域中, 同时也是有机合成中重要的中间体和催化剂. 基于此类化合物的重要作用, 手性有机硒化合物的合成一直是有机化学方向热点研究领域之一. 近年来, 发展绿色经济的手性有机硒化合物合成方法得到了广泛关注. 主要综述了近十年基于不同催化体系下合成手性有机硒化合物的研究进展, 主要分为无金属催化、金属催化、光催化三种反应体系来归纳总结, 并对手性有机硒化合物合成的挑战和未来发展方向进行了探讨.

关键词: 无金属催化, 金属催化, 光催化, 手性有机硒化合物

Chiral organoselenium compounds are widely found in bioactive molecules, natural products, pharmaceutical agents, and functional materials. They also serve as important intermediates and catalysts in organic synthesis. Given the significance of such compounds, the synthesis of chiral organoselenium compounds has long been a hot research topic in organic chemistry. In recent years, the development of environmentally benign and cost-effective methods for synthesizing chiral organoselenium compounds has attracted considerable attention. The research progress in the synthesis of chiral organoselenium compounds under different catalytic systems over the past decade is reviewed. This review is organized into three catalytic systems: metal-free catalysis, metal catalysis, and photocatalysis, and the research progress of each system is discussed in detail. Additionally, the challenges and future directions in the synthesis of chiral organoselenium compounds are also discussed.

Key words: metal-free catalysis, metal-catalysis, photocatalysis, chiral organoselenium compounds

引用此文

郭艳辉, 屈红恩, 梁佩. 手性有机硒化合物的合成研究进展[J]. 有机化学, 2026, 46(3): 786-805.

Yanhui Guo, Hongen Qu, Pei Liang. Recent Advances in Synthesis of Chiral Organoselenium Compounds[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 786-805.

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

分享此文

图/表 30

图式1. 代表性的含硒功能分子

Scheme 1. Representative selenium-containing functional molecules

图式2. (DHQD)2PHAL催化烯酸的对映选择性硒内酯化反应

Scheme 2. (DHQD)2PHAL-catalyzed enantioselective selenolactonization of alkenoic acids

图式3. 有机催化3-吡咯基氧化吲哚的不对称硒化反应

Scheme 3. Organocatalytic asymmetric selenenylation of 3-pyrrolyl-oxindoles

图式4. 手性路易斯碱/布鲁斯特酸共催化烯基二醇的对映选择性硒醚化反应

Scheme 4. Co-catalysis of enantioselective selenoetherification of olefinic diols by chiral Lewis bases/Brønsted acids

图式5. 有机催化α,β-不饱和酮与硒代磺酸酯的不对称加成反应

Scheme 5. Organocatalytic asymmetric addition reaction of α,β-unsaturated ketones with selenosulfonates

图式6. 手性布鲁斯特酸催化氧杂环丁烷分子内去对称化反应

Scheme 6. Chiral Brønsted acid-catalyzed intramolecular desymmetrization of oxetanes

图式7. 有机催化非末端α,β-不饱和酮的不对称硒磺酰化反应

Scheme 7. Organocatalytic asymmetric selenosulfonylation of non-terminal α,β-unsaturated ketones

图式8. 手性双功能NHC/硫脲催化烯酮的不对称硒迈克尔加成反应

Scheme 8. Chiral bifunctional NHC-thiourea-catalyzed asymmetric seleno-Michael addition of enones

图式9. 手性路易斯碱催化1,1-二取代烯烃对映选择性硒环化反应

Scheme 9. Chiral Lewis base catalyzed enantioselective seleno- cyclization of 1,1-disubstituted alkenes

图式10. NHC催化溴代烯醛和芳基硒代甲酰胺的不对称硒迈克尔加成反应

Scheme 10. N-Heterocyclic carbene-catalyzed enantioselective seleno-Michael addition with bromoenals and arylselenocarboxamides

图式11. 有机催化炔烃的阻转选择性氢硒化反应

Scheme 11. Organocatalytic atroposelective hydroselenation of alkynes

图式12. 手性硫化物与非手性磺酸共催化联烯醇的不对称亲电串联硒化/半频哪醇重排反应

Scheme 12. Chiral sulfide and achiral sulfonic acid cocatalyzed enantioselective electrophilic tandem selenylation semipinacol rearrangement of allenols

图式13. 有机催化1-(1-芳基乙烯基)环丁醇的不对称亲电串联硒化/半频哪醇重排反应

Scheme 13. Organocatalytic asymmetric electrophilic tandem selenylation semipinacol rearrangement of 1-(1-arylvinyl)cyclobutanols

图式14. 碳酸铯促进手性苄基三甲基铵盐与二硒醚的偶联反应

Scheme 14. Cs2CO3 promoted coupling reaction of chiral benzylic trimethylammonium salts with diselenides

图式15. 碱促进元素硒与手性苄基季铵盐合成手性二苄基二硒醚

Scheme 15. Base-promoted synthesis of chiral dibenzyl diselenides from elemental selenium and chiral benzyl quaternary ammonium salts

图式16. 立体选择性硒-迈克尔加成反应制备手性β-硒代-α-氨基酸

Scheme 16. Stereoselective Se-Michael addition preparation of chiral β-selenium α-amino acids

图式17. 铑催化杂环烯烃的不对称氢硒化反应

Scheme 17. Rhodium-catalyzed enantioselective hydroselenation of heterobicyclic alkenes

图式18. 镍催化β-酮酯的不对称硒氰化反应

Scheme 18. Nickel-catalyzed asymmetric selenocyanation of β-ketoesters

图式19. 手性钴催化烯丙基硒醚和α-重氮吡唑甲酰胺的不对称[2,3]-σ迁移重排反应

Scheme 19. Chiral cobalt(II) complex catalyzed asymmetric [2,3]-sigmatropic rearrangement of allylic selenides with α-diazo pyrazoleamides

图式20. 铑催化苯乙烯的不对称氢硒化反应

Scheme 20. Rhodium-catalyzed enantioselective hydroselena- tion of styrenes

图式21. 铬催化β-羟基硒醚的非对映选择性及对映选择性合成

Scheme 21. Cr-catalyzed diastereo- and enantioselective synthesis of β-hydroxy selenides

图式22. 铜催化硒醇和α-取代的α,β-不饱和硫代酰胺的不对称共轭加成/质子化反应

Scheme 22. Copper-catalyzed asymmetric conjugate addition/protonation with selenols and α-substituted α,β-unsaturated thioamides

图式23. 铑催化1-芳基异喹啉的轴手性选择性C—H硒化反应

Scheme 23. Rh(III)-catalyzed atroposelective C—H selenylation of 1-aryl isoquinolines

图式24. 铑催化1-炔基吲哚的不对称氢硒化反应

Scheme 24. Rhodium-catalyzed asymmetric hydroselenation of 1-alkynylindoles

图式25. 铑催化1-芳基异喹啉的阻转选择性C—H硒化反应

Scheme 25. Rhodium-catalyzed atroposelective C—H selenylation of 1-aryl isoquinoline

图式26. 铑催化环丙烯的不对称保环氢硒化反应

Scheme 26. Rhodium-catalyzed asymmetric ring-retentive hydroselenation of cyclopropenes.

图式27. 铑催化α-重氮酯的不对称插入反应

Scheme 27. Rhodium-catalyzed asymmetric insertion reaction of α-diazoesters

图式28. 铜催化2-酰基咪唑的不对称α-硒化反应

Scheme 28. Copper(I)-catalyzed asymmetric α-selenenylation of 2-acylimidazoles

图式29. 立体特异性铝催化异硒氰酸酯和手性氮杂环丙烷的串联C—N/C—Se键形成反应

Scheme 29. Stereospecific Al-catalysed tandem C—N/C—Se bond formation of isoselenocyanates with aziridines

图式30. 可见光催化合成手性α-硒代氨基酸衍生物

Scheme 30. Visible-light photoredox synthesis of chiral α-selenoamino acids

参考文献 70

[1]	Berzelius, J. J. Afh. Fys., Kemi Mineral. 1818, 6, 42.
[2]	Atkins, J. F.; Gesteland, R. F. Nature 2000, 407, 463. doi: 10.1038/35035189
[3]	Winkel, L. H. E.; Johnson, C. A.; Lenz, M.; Grundl, T.; Leupin, O. X.; Amini, M.; Charlet, L. Environ. Sci. Technol. 2012, 46, 571. doi: 10.1021/es203434d
[4]	Reich, H. J.; Hondal, R. J. ACS Chem. Biol. 2016, 11, 821. doi: 10.1021/acschembio.6b00031 pmid: 26949981
[5]	Thiry, C.; Ruttens, A.; De Temmerman, L.; Schneider, Y.-J.; Pus- semier, L. Food Chem. 2012, 130, 767. doi: 10.1016/j.foodchem.2011.07.102
[6]	Sonet, J.; Mosca, M.; Bierla, K.; Modzelewska, K.; Flis-Borsuk, A.; Suchocki, P.; Ksiazek, I.; Anuszewska, E.; Bulteau, A.-L.; Szpunar, J.; Lobinski, R.; Chavatte, L. Nutrients 2019, 11, 1524. doi: 10.3390/nu11071524
[7]	Deng, H., Liu, H., Yang, Z.; Bao, M.; Lin, X.; Han, J.; Qu, C. Biol. Trace Elem. Res. 2022, 200, 4238. doi: 10.1007/s12011-021-03022-4
[8]	Genchi, G.; Lauria, G.; Catalano, A.; Sinicropi, M. S.; Carocci, A. Int. J. Mol. Sci. 2023, 24, 2633. doi: 10.3390/ijms24032633
[9]	Corrigan, J. F. J. Am. Chem. Soc. 2007, 129, 5782.
[10]	Paulmier, C. Selenium Reagents and Intermediates in Organic Synthesis, Elsevier, Amsterdam, The Netherlands, 1986, p. 463.
[11]	du Mont, W.-W. Angew. Chem., Int. Ed. 1988, 27, 444.
[12]	Back, G. T. Organoselenium Chemistry: A Practical Approach, OUP Oxford, Oxford, UK, 1999, p. 295.
[13]	Vinogradova, E. V.; Zhang, C.; Spokoyny, A. M.; Pentelute, B. L.; Buchwald, S. L. Nature 2015, 526, 687. doi: 10.1038/nature15739
[14]	Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004, 104, 6255. doi: 10.1021/cr0406559
[15]	Manna, D.; Roy, G.; Mugesh, G. Acc. Chem. Res. 2013, 46, 2706. doi: 10.1021/ar4001229
[16]	Liang, Y.; Zhao, X. ACS Catal. 2019, 9, 6896. doi: 10.1021/acscatal.9b01900
[17]	Brutchey, R. L. Acc. Chem. Res. 2015, 48, 2918. doi: 10.1021/acs.accounts.5b00362
[18]	Patra, A.; Wijsboom, Y. H.; Leitus, G.; Bendikov, M. Chem. Mater. 2011, 23, 896. doi: 10.1021/cm102395v
[19]	Guan, B.; Yan, R.; Li, R.; Zhang, X. Int. J. Nanomed. 2018, 13, 7473. doi: 10.2147/IJN
[20]	Yadav, S.; Ramesh, K.; Reddy, O. S.; Karthika, V.; Kumar, P.; Jo, S. H.; Yoo, S. I.; Park, S. H.; Lim, K. T. Pharmaceutica 2023, 15, 1159. doi: 10.3390/ph15091159
[21]	Liu, S.; Wei, W.; Wang, J.; Chen, T. J. Nanobiotechnol. 2023, 21, 96. doi: 10.1186/s12951-023-01825-2
[22]	Ma, Y.; Liu, R.; Gong, X.; Li, Z.; Huang, Q.; Wang, H.; Song, G. J. Agric. Food Chem. 2006, 54, 7724. doi: 10.1021/jf0609328
[23]	Laskowska, A.; Pacula-Miszewska, A. J.; Obieziurska-Fabisiak, M.; Jastrzebska, A.; Gach-Janczak, K.; Janecka, A.; Scianowski, J. RSC Adv. 2023, 13, 14698. doi: 10.1039/d3ra02475j pmid: 37197685
[24]	Xiong, Z.; Lin, H.; Li, H.; Zou, B.; Xie, B.; Yu, Y.; He, L.; Chen, T. Adv. Funct. Mater. 2023, 33, 2212970. doi: 10.1002/adfm.v33.17
[25]	Huang, Y.; Fu, Y.; Li, M.; Jiang, D.; Kutyreff, C. J.; Engle, J. W.; Lan, X.; Cai, W.; Chen, T. Angew. Chem., Int. Ed. 2020, 59, 4406. doi: 10.1002/anie.v59.11
[26]	Li, X.; Wang, G.; Zhao, J.; Ding, H.; Cunningham, C.; Chen, F.; Flynn, D. C.; Reed, E.; Li, Q. Q. Cell. Mol. Life Sci. 2005, 62, 894. doi: 10.1007/s00018-005-5027-1 pmid: 15868412
[27]	Marini, F.; Sternativo, S. Synlett 2013, 24, 11. doi: 10.1055/s-00000083
[28]	Singh, F. V.; Wirth, T. Catal. Sci. Technol. 2019, 9, 1073. doi: 10.1039/C8CY02274G
[29]	Liao, L.; Zhao, X. Acc. Chem. Res. 2022, 55, 2439. doi: 10.1021/acs.accounts.2c00201
[30]	Sun, K.; Wang, X.; Li, C.; Wang, H.; Li, L. Org. Chem. Front. 2020, 7, 3100. doi: 10.1039/D0QO00849D
[31]	Ma, Y.-T.; Liu, M.-C.; Zhou, Y.-B.; Wu, H.-Y. Adv. Synth. Catal. 2021, 363, 5386. doi: 10.1002/adsc.v363.24
[32]	Protti, S.; Fagnoni, M. ACS Org. Inorg. Au 2022, 2, 455. doi: 10.1021/acsorginorgau.2c00033
[33]	Lu, L.; Huang, D.; Wang, Z.; Wang, X.; Wu, X. Adv. Synth. Catal. 2023, 365, 2310. doi: 10.1002/adsc.v365.14
[34]	Nakamura, S.; Aoki, T.; Ogura, T.; Wang, L.; Toru, T. J. Org. Chem. 2004, 69, 8916. pmid: 15575774
[35]	Tiecco, M.; Testaferri, L.; Santi, C.; Tomassini, C.; Bonini, R.; Marini, F.; Bagnoli, L.; Temperini, A. Org. Lett. 2004, 6, 4751. doi: 10.1021/ol048001+
[36]	Brondani, P. B.; Guilmoto, N. M. A. F.; Dudek, H. M.; Fraaije, M. W.; Andrade, L. H. Tetrahedron 2012, 68, 10431. doi: 10.1016/j.tet.2012.09.087
[37]	Lai, S.; Liang, X.; Zeng, Q. Chem.-Eur. J. 2024, 30, e202304067. doi: 10.1002/chem.v30.16
[38]	Stadel, J. T.; Back, T. G. Chem.-Eur. J. 2024, 30, e202304074. doi: 10.1002/chem.v30.21
[39]	Jian, Y.; Singh, T.; Andersson, P. G.; Zhou, T. Molecules 2024, 29, 3685. doi: 10.3390/molecules29153685
[40]	Li, H.-S.; Lu, S.-C. Adv. Synth. Catal. 2025, 367, e202500347. doi: 10.1002/adsc.v367.15
[41]	Pluim, H.; Wynberg, H. Tetrahedron Lett. 1979, 20, 1251. doi: 10.1016/S0040-4039(01)86116-5
[42]	Tian, H.; Zhang, H.-M.; Yin, L. Angew. Chem., Int. Ed. 2023, 62, e202301422. doi: 10.1002/anie.v62.24
[43]	Niu, W.; Yeung, Y.-Y. Org. Lett. 2015, 17, 1660. doi: 10.1021/acs.orglett.5b00377
[44]	You, Y.; Wu, Z.-J.; Wang, Z.-H.; Xu, X.-Y.; Zhang, X.-M.; Yuan, W.-C. J. Org. Chem. 2015, 80, 8470. doi: 10.1021/acs.joc.5b01491
[45]	See, J. Y.; Yang, H.; Zhao, Y.; Wong, M. W.; Ke, Z.; Yeung, Y.-Y. ACS Catal. 2018, 8, 850. doi: 10.1021/acscatal.7b03510
[46]	Luo, S.; Zhang, N.; Wang, Z.; Yan, H. Org. Biomol. Chem. 2018, 16, 2893. doi: 10.1039/C8OB00359A
[47]	Zhang, R.; Guo, W.; Duan, M.; Houk, K. N.; Sun, J. Angew. Chem., Int. Ed. 2019, 58, 18055. doi: 10.1002/anie.v58.50
[48]	Chen, Z.; Hu, F.; Huang, S.; Zhao, Z.; Mao, H.; Qin, W. J. Org. Chem. 2019, 84, 8100. doi: 10.1021/acs.joc.9b00973
[49]	Li, E.; Chen, J.; Huang, Y. Angew. Chem., Int. Ed. 2022, 61, e202202040. doi: 10.1002/anie.v61.23
[50]	Cao, R.; Yu, L.; Huo, Y.; Li, Y.; Xue, X.; Chen, Z. Org. Lett. 2022, 24, 4093. doi: 10.1021/acs.orglett.2c01731
[51]	Long, H.; Zhao, S.; Jian, C.; Wu, X.; Lu, F.; Liao, M.; Che, F.; Wu, X.; Chi, Y. R. Sci. China Chem. 2024, 67, 2199. doi: 10.1007/s11426-023-1909-5
[52]	Wang, Y.-X.; Wang, J.-R.; Cui, C.; Wang, Z.; Lu, Y.; Yang, X.-H. ACS Catal. 2025, 15, 4051. doi: 10.1021/acscatal.4c07281
[53]	Cao, R.-F.; Su, R.; Wei, Z.-W.; Li, Z.-L.; Zhu, D.; Huo, Y.-X.; Xue, X.-S.; Chen, Z.-M. Nat. Commun. 2025, 16, 2147. doi: 10.1038/s41467-025-57381-w
[54]	Cao, R.-F.; Wei, Z.-W.; Li, S.-K.; Ding, T.-M.; Ke, H.; Chen, Z.-M. Chem. Commun. 2025, 61, 8532. doi: 10.1039/D5CC01919B
[55]	Li, F.; Wang, D.; Chen, H.; He, Z.; Zhou, L.; Zeng, Q. Chem. Commun. 2020, 56, 13029. doi: 10.1039/D0CC05633B
[56]	Chen, F.; Li, F.; Zeng, Q. Eur. J. Org. Chem. 2021, 2021, 5605. doi: 10.1002/ejoc.v2021.41
[57]	Oroz, P.; Navo, C. D.; Avenoza, A.; Busto, J. H.; Corzana, F.; Jiménez-Osés, G.; Peregrina, J. M. Org. Lett. 2021, 23, 1955. doi: 10.1021/acs.orglett.0c03832
[58]	Li, S.; Yang, Q.; Bian, Z.; Wang, J. Org. Lett. 2020, 22, 2781. doi: 10.1021/acs.orglett.0c00762
[59]	Wu, D.; Qiu, J.; Li, C.; Yuan, L.; Yin, H.; Chen, F.-X. J. Org. Chem. 2020, 85, 934. doi: 10.1021/acs.joc.9b02786
[60]	Lin, X.; Tan, Z.; Yang, W.; Yang, W.; Liu, X.; Feng, X. CCS Chem. 2021, 3, 1423. doi: 10.31635/ccschem.020.202000345
[61]	Slocumb, H. S.; Nie, S.; Dong, V. M.; Yang, X.-H. J. Am. Chem. Soc. 2022, 144, 18246. doi: 10.1021/jacs.2c08475
[62]	Xia, X.; Wang, Z. ACS Catal. 2022, 12, 11152. doi: 10.1021/acscatal.2c03271
[63]	Zheng, D.; Xie, P.; Zhao, F.; Zheng, C.; Gu, Q.; You, S. ACS Catal. 2024, 14, 6009. doi: 10.1021/acscatal.4c01082
[64]	Kang, Y.; Wang, F.; Li, X. ACS Catal. 2024, 14, 13055. doi: 10.1021/acscatal.4c03710
[65]	Wang, Y.; Yu, S.; Li, X. Org. Chem. Front. 2025, 12, 816. doi: 10.1039/D4QO01905A
[66]	Cui, C.; Li, Q.; Wang, Z.; Lu, Y.; Yang, X.-H. ACS Catal. 2025, 15, 8855. doi: 10.1021/acscatal.5c02081
[67]	He, X.; Fu, Y.; Xi, R.; Zhang, C.; Lan, K.; Su, Z.; Wang, F.; Feng, X.; Liu, X. Angew. Chem., Int. Ed. 2025, 64, e202417636. doi: 10.1002/anie.v64.5
[68]	Tian, H.; Huang, X.; Xiao, J.-Z.; Yin, L. JACS Au 2025, 5, 578. doi: 10.1021/jacsau.4c01182 pmid: 40017750
[69]	Satheesh, V.; Srivastava, H. K.; Kumar, S. V.; Sengoden, M.; Punniyamurthy, T. Adv. Synth. Catal. 2019, 361, 55. doi: 10.1002/adsc.v361.1
[70]	Jiang, M.; Yang, H.; Fu, H. Org. Lett. 2016, 18, 1968. doi: 10.1021/acs.orglett.6b00489 pmid: 27093481