Research Progress on Catalytic Asymmetric Synthesis of Chiral Organoselenium Compounds

doi:10.6023/A25080280

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (10): 1237-1251.DOI: 10.6023/A25080280 Previous Articles Next Articles

Review

手性有机硒化合物的催化不对称合成研究进展

李晖^a^,^*(), 殷亮^b^,^*()

^a 运城学院应用化学系运城 044000
^b 中国科学院上海有机化学研究所先进氟氮材料全国重点实验室上海 200032

投稿日期:2025-08-15 发布日期:2025-09-15
通讯作者: 李晖, 殷亮

作者简介:

李晖, 运城学院应用化学系副教授. 本科毕业于南开大学; 硕士毕业于天津大学(导师: 姜申德教授). 主要从事铜催化反应研究和药物中间体合成工艺研究等.

殷亮, 中国科学院上海有机化学研究所研究员、课题组长. 本科和硕士毕业于南开大学; 博士毕业于东京大学(导师: Masakatsu Shibasaki教授和Motomu Kanai教授); 于哈佛大学(导师: EJ Corey教授)和日本微生物化学研究所(导师: Masakatsu Shibasaki教授)开展博士后研究. 目前主要从事一价铜催化的不对称C—C键和C—X键成键反应研究.

基金资助:
国家自然科学基金(22271302)

Research Progress on Catalytic Asymmetric Synthesis of Chiral Organoselenium Compounds

Hui Li^a^,^*(), Liang Yin^b^,^*()

^a Department of Applied Chemistry, Yuncheng University, Yuncheng 044000
^b State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Received:2025-08-15 Published:2025-09-15
Contact: Hui Li, Liang Yin
Supported by:
National Natural Science Foundation of China(22271302)

Chiral selenium-bearing organic compounds have found application in a wide range of fields, including synthetic chemistry, material science, medicinal chemistry, and agricultural chemistry. Meanwhile, they serve as powerful chiral ligands or organocatalysts in asymmetric catalysis. Therefore, asymmetric synthesis of chiral organoselenides has attracted considerable attention from the chemical community. Catalytic asymmetric C—Se bond coupling reaction between selenium resources and the corresponding reaction partners are appreciated as one of the most straightforward and powerful strategies for the construction of chiral organoselenium compounds. Recent research progress on catalytic asymmetric synthesis of chiral organoselenium compounds via this strategy is summarized. Based on the nature of selenium resources, this review is divided into two sections: catalytic asymmetric coupling of electrophilic selenium reagents with nucleophilic partners and catalytic asymmetric coupling of nucleophilic selenium reagents with electrophilic partners. Mechanisms and substrate scopes of some representative reactions are also briefly described.

Key words: chiral organoselenium compound, asymmetric catalysis, electrophilic selenium reagent, nucleophilic selenium reagent, construction of C—Se bond

Cite this article

Hui Li, Liang Yin. Research Progress on Catalytic Asymmetric Synthesis of Chiral Organoselenium Compounds[J]. Acta Chimica Sinica, 2025, 83(10): 1237-1251.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 26

Figure 1. Representative electrophilic and nucleophilic selenization reagents

Scheme 1. Catalytic asymmetric synthesis of chiral organoselenium compounds with electrophilic selenium sources

Scheme 2. Desymmetrizing asymmetric selenoetherification through supramolecular catalysis

Scheme 3. Enantioselective selenolactonization with a C2-symmetric sulfur-based catalyst

Scheme 4. Enantioselective selenocyclization of 1,1-disubstituted alkenes for the synthesis of 4H-3,1-benzoxazines

Scheme 5. Enantioselective selenosulfonylation of α,β-unsaturated ketones

Scheme 6. Asymmetric selenylation-semipinacol rearrangement of enols and allenols

Scheme 7. Rhodium-catalyzed atroposelective selenylation of 1-aryl isoquinolines

Scheme 8. Enantioselective α-selenylation of carbonyl-containing N- and O-heterocycle compounds

Scheme 9. Nickel-catalyzed enantioselective α-selenocyanation of β-ketoesters

Scheme 10. Copper(I)-catalyzed enantioselective α-selenenylation of 2-acylimidazoles

Scheme 11. Copper(I)-catalyzed enantioselective vinylogous selenenylation

Scheme 12. Asymmetric intramolecular tandem oxa-Michael addition- selenocyanation of alkylidene β-ketoesters

Scheme 13. Asymmetric carbene insertion into Se—S bonds under Rh(II)/guanidine synergistic catalysis

Scheme 14. Catalytic asymmetric synthesis of chiral organoselenium compounds with nucleophilic selenium sources

Scheme 15. Rhodium-catalyzed enantioselective hydroselenation of heterobicyclic alkenes

Scheme 16. Rhodium-catalyzed enantioselective hydroselenation of styrenes

Scheme 17. Rhodium-catalyzed enantioselective hydroselenation of cyclopropenes

Scheme 18. Rhodium-catalyzed atroposelective hydroselenation of 1-alkynylindoles

Scheme 19. Organocatalytic atroposelective hydroselenation of 1-alkynylnaphthalen-2-ols

Scheme 20. Organocatalytic asymmetric addition of selenol to ketimine

Scheme 21. Chiral N-heterocyclic carbene-catalyzed asymmetric Michael addition of alkyl selenols to α,β-unsaturated carbonyls

Scheme 22. Copper(I)-catalyzed asymmetric conjugate addition of selenols to α,β-unsaturated thioamides

Scheme 23. Carbene-catalyzed stereoselective [3＋3] annulations between selenocarboxamides and bromoenals

Scheme 24. Cobalt(II)-catalyzed asymmetric [2,3]-sigmatropic rearrangement of allylic selenides with α-diazo pyrazoleamides

Scheme 25. Chiral Brønsted acid-catalyzed asymmetric desymmetrization intramolecular ring-opening of oxetanes

References 54

[4]	(c) Ali W.; Benedetti R.; Handzlik J.; Zwergel C.; Battistelli C. Drug Discovery Today 2021, 26, 256. pmid: 38299513
[5]	(a) Shi Z.; Zhang H.; Khan K.; Cao R.; Xu K.; Zhang H. Nano. Res. 2022, 15, 104.
	(b) Gorska S.; Maksymiuk A.; Turlo J. Appl. Sci. 2021, 11, 3717.
	(c) Wadhwani S. A.; Shedbalkar U.; Singh R.; Chopade B. A. Appl. Microbiol. Biot. 2016, 100, 2555.
[6]	(a) Singh F. V.; Wirth T. Catal. Sci. Technol. 2019, 9, 1073.
	(b) Liao L.; Zhao X.; Acc. Chem. Res. 2022, 55, 2439.
[7]	(a) Wirth T. Angew. Chem., Int. Ed. 2000, 39, 3740.
	(b) Tiecco M.; Testaferri L.; Marini F.; Bagnoli L.; Santi C.; Temperini A.; Sternativo S.; Tomassini C. Phosphorus Sulfur Silicon Relat. Elem. 2005, 180, 729.
	(c) Zhu C.; Huang Y. Curr. Org. Chem. 2006, 10, 1905.
	(d) Rafiński Z.; Ścianowski J. Tetrahedron: Asymmetry 2008, 19, 1237.
[1]	Labunskyy V. M.; Hatfield D. L.; Gladyshev V. N. Roles. Physiol. Rev. 2014, 94, 739.
[2]	(a) Mukherjee A. J.; Zade S. S.; Singh H. B.; Sunoj R. B. Chem. Rev. 2010, 110, 4357. doi: 10.1021/cr900352j pmid: 20384363
	(b) Wang C.; Dong H.; Hu W.; Liu Y.; Zhu D. Chem. Rev. 2012, 112, 2208. pmid: 20384363
	(c) Nogueira C. W.; Rocha J. B. T. Arch. Toxicol. 2011, 85, 1313. pmid: 20384363
[3]	(a) Cheng K.; Sun Y.; Liu B.; Ming J.; Wang L.; Xu C.; Xiao Y.; Zhang C.; Shang L. Foods 2023, 12, 3773.
	(b) Hou W.; Dong H.; Zhang X.; Wang Y.; Su L.; Xu H. Drug Discovery Today 2022, 27, 2268.
	(c) Hou W.; Xu H. J. Med. Chem. 2022, 65, 4436.
[4]	(a) Angelone T.; Rocca C.; Lionetti V.; Penna C.; Pagliaro P. Antioxid. Redox Sign. 2024, 40, 369. doi: 10.1089/ars.2023.0285 pmid: 38299513
	(b) Radomska D.; Czarnomysy R.; Radomski D.; Bielawski K. J. Mol. Sci. 2021, 22, 1009. pmid: 38299513
[7]	(e) Uehlin L.; Wirth T. Phosphorus Sulfur Silicon Relat. Elem. 2009, 184, 1374.
[8]	(a) Chen S.; Fan C.; Xu Z.; Pei M.; Wang J.; Zhang J.; Zhang Y.; Li J.; Lu J.; Peng C.; Wei F. Nat. Commun. 2024, 15, 769.
	(b) Ma Y.-T.; Liu M.-C.; Zhou Y.-B.; Wu H.-Y. Adv. Synth. Catal. 2021, 363, 5386.
	((c) Feng S.; Zhong X.; Chen J.; Zhang Z.; Gu G.; Wang J.; Guo Y.; Ma J.; Zhang S. Chin. J. Org. Chem. 2025, 45, 2425 (in Chinese).
	(冯书晓, 钟轩, 陈嘉豪, 张宗洛, 谷广娜, 王俊岭, 郭亚菲, 马军营, 张守仁, 有机化学, 2025, 45, 2425.) doi: 10.6023/cjoc202411011
[9]	(a) Lai S.; Liang X.; Zeng Q. Chem.-Eur. J. 2024, 30, e202304067.
	(b) Stadel J. T.; Back T. G. Chem.-Eur. J. 2024, 30, e202304074.
	(c) Jian Y.; Singh T.; Andersson P. G.; Zhou T. Molecules 2024, 29, 3685.
[10]	(a) Xia X.; Wang Z. ACS Catal. 2022, 12, 11152. pmid: 27862465
	(b) Zhang T.; Cheng L.; Hameed S.; Liu L.; Wang D.; Chen Y.-J.; Chem. Commun. 2011, 47, 6644. pmid: 27862465
	(c) Sternativo S.; Calandriello A.; Costantino F.; Testaferri L.; Tiecco M.; Marini F. Angew. Chem., Int. Ed. 2011, 50, 9382. doi: 10.1002/anie.201104819 pmid: 27862465
	(d) Buyck T.; Wang Q.; Zhu J. Angew. Chem., Int. Ed. 2013, 52, 12714. pmid: 27862465
	(e) Clemenceau A.; Wang Q.; Zhu J. Chem.-Eur. J. 2016, 22, 18368. doi: 10.1002/chem.201604781 pmid: 27862465
	(f) Shinichi Y.; Mayumi T.; Shoko Y. J. Org. Chem. 1996, 61, 4046. pmid: 27862465
	(g) Miyake Y.; Oda M.; Oyamada A.; Takada H.; Ohe K.; Uemura S. J. Organomet. Chem. 2000, 611, 475. pmid: 27862465
	(h) Marcos V.; Alemán J.; Ruano J. L. G.; Marini F.; Tiecco M. Org. Lett. 2011, 13, 3052. pmid: 27862465
[11]	(a) Guo H.-C.; Lin J.; Liu M.-C.; Zhou Y.-B.; Wu H.-Y. Tetrahedron Lett. 2023, 132, 154825.
	(b) Wang X.; Lei J.; Guo S.; Zhang Y.; Ye Y.; Tang S.; Sun K. Chem. Commun. 2022, 58, 1526.
	((c) Yu T.; Song D.; Xu Y.; Liu B.; Chen N.; Liu Y. Chin. J. Org. Chem. 2022, 42, 4202 (in Chinese).
	(于婷婷, 宋冬雪, 许颖, 刘冰, 陈宁, 刘颖杰, 有机化学, 2022, 42, 4202.) doi: 10.6023/cjoc202204037
[12]	Denmark S. E.; Kalyani D.; Collins W. R. J. Am. Chem. Soc. 2010, 132, 15752. doi: 10.1021/ja106837b pmid: 20961070
[13]	Guan H.; Wang H.; Huang D.; Shi Y. Tetrahedron 2012, 68, 2728.
[14]	Wei Q.; Wang Y.-Y.; Du Y.-L.; Gong L.-Z. Beilstein J. Org. Chem. 2013, 9, 1559.
[15]	Zhang H.; Lin S.; Jacobsen E. N. J. Am. Chem. Soc. 2014, 136, 16485. doi: 10.1021/ja510113s pmid: 25380129
[16]	Niu W.; Yeung Y.-Y. Org. Lett. 2015, 17, 1660.
[17]	See J. Y.; Yang H.; Zhao Y.; Wong M. W.; Ke Z.; Yeung Y.-Y. ACS Catal. 2018, 8, 850.
[18]	Jana S.; Verma A.; Rathore V.; Kumar S. Synlett 2019, 30, 1667.
[19]	Cao R.-F.; Yu L.; Huo Y.-X.; Li Y.; Xue X.-S.; Chen Z.-M. Org. Lett. 2022, 24, 4093.
[20]	Luo S.; Zhang N.; Wang Z.; Yan H. Org. Biomol. Chem. 2018, 16, 2893.
[21]	Chen Z.; Hu F.; Huang S.; Zhao Z.; Mao H.; Qin W. J. Org. Chem. 2019, 84, 8100.
[22]	Cao R.-F.; Wei Z.-W.; Li S. K.; Ding T. M.; Ke H.; Chen Z.-M. Chem. Commun. 2025, 61, 8532.
[23]	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.
[24]	Zheng D.-S.; Xie P.-P.; Zhao F.; Zheng C.; Gu Q.; You S.-L. ACS Catal. 2024, 14, 6009.
[25]	(a) Kang Y.-S.; Zhang P.; Li M.-Y.; Chen Y.-K.; Xu H.-J.; Zhao J.; Sun W.-Y.; Yu J.-Q.; Lu Y. Angew. Chem., Int. Ed. 2019, 58, 9099.
	(b) Xu H.; Gu Y.; Zhang S.; Xiong H.; Ma F.; Lu F.; Ji Q.; Liu L.; Ma P.; Hou W.; Yang G.; Lerner R. A. Angew. Chem., Int. Ed. 2020, 59, 13273.
[26]	Wang Y.; Yu S.; Li X. Org. Chem. Front. 2025, 12, 816.
[27]	(a) Tiecco M.; Carlone A.; Sternativo S.; Marini F.; Bartoli G.; Melchiorre P. Angew. Chem., Int. Ed. 2007, 46, 6882.
	(b) Sundén H.; Rios R.; Córdova A. Tetrahedron Lett. 2007, 48, 7865.
	(c) Giacalone F.; Gruttadauria M.; Agrigento P.; Campisciano V.; Noto R. Catal. Commun. 2011, 16, 75.
	(d) Kamlar M.; Veselý J. Tetrahedron: Asymmetry 2013, 24, 254.
	(e) Burés J.; Dingwall P.; Armstrong A.; Blackmond D. G. Angew. Chem., Int. Ed. 2014, 53, 8700.
	(f) Movassagh B.; Takallou A. Synlett 2015, 26, 2247.
[28]	You Y.; Wu Z.-J.; Wang Z.-H.; Xu X.-Y.; Zhang X.-M.; Yuan W.-C. J. Org. Chem. 2015, 80, 8470.
[29]	Caruano J.; Muccioli G. G.; Robiette R. Org. Biomol. Chem. 2016, 14, 10134. pmid: 27748489
[30]	Singha Roy S. J.; Mukherjee S. Org. Biomol. Chem. 2017, 15, 6921.
[31]	Zhang Y.; Wu X.-Y.; Han J.; Wong H. N. C. Tetrahedron Lett. 2020, 61, 151559.
[32]	Haider V.; Zebrowski P.; Michalke J.; Monkowius U.; Waser M. Org. Biomol. Chem. 2022, 20, 824.
[33]	Wu D.; Qiu J.; Li C.; Yuan L.; Yin H.; Chen F.-X. J. Org. Chem. 2020, 85, 934.
[34]	Tian H.; Huang X.; Xiao J.-Z.; Yin L. JACS Au 2025, 5, 578. doi: 10.1021/jacsau.4c01182 pmid: 40017750
[35]	Tian H.; Wang Y.-F.; Yin L. CCS Chem. 2025, doi: 10.31635/ccschem.025.202505926.
[36]	Gao Y.; Fu Z.; Wu D.; Yin H.; Chen F.-X. Asian J. Org. Chem. 2022, 11, e202100649.
[37]	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.
[38]	Li S.; Yang Q.; Bian Z.; Wang J. Org. Lett. 2020, 22, 2781.
[39]	Slocumb H. S.; Nie S.; Dong V. M.; Yang X.-H. J. Am. Chem. Soc. 2022, 144, 18246.
[40]	Phun G. S.; Slocumb H. S.; Ruud K. J.; Nie S.; Antonio C.; Furche F.; Dong V. M.; Yang X.-H. Chem. Sci. 2024, 15, 20523.
[41]	Shan C.; Luo X.; Luo X.; Long R. Dalton Trans. 2025, 54, 3714.
[42]	Cui C.; Li Q.; Wang Z.; Lu Y.; Yang X.-H. ACS Catal. 2025, 15, 8855.
[43]	Kang Y.; Wang F.; Li X. ACS Catal. 2024, 14, 13055.
[44]	Wang Y.-X.; Wang J.-R.; Cui C.; Wang Z.; Lu Y.; Yang X.-H. ACS Catal. 2025, 15, 4051.
[45]	Ingle G. K.; Mormino M. G.; Wojtas L.; Antilla J. C. Org. Lett. 2011, 13, 4822.
[46]	Oyamada Y.; Fujii M.; Takehara T.; Suzuki T.; Nakamura S. ACS Catal. 2024, 14, 3411.
[47]	Pluim H.; Wynberg H. Tetrahedron Lett. 1979, 20, 1251.
[48]	Li E.; Chen J.; Huang Y. Angew. Chem., Int. Ed. 2022, 61, e202202040.
[49]	Tian H.; Zhang H.-M.; Yin L. Angew. Chem., Int. Ed. 2023, 62, e202301422.
[50]	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.
[51]	Lin X.; Tan Z.; Yang W.; Yang W.; Liu X.; Feng X. CCS Chem. 2021, 3, 1423.
[52]	Yang M.; Zhu C.; Yuan F.; Huang Y.; Pan Y. Org. Lett. 2005, 7, 1927.
[53]	Ingle G.; Mormino M. G.; Antilla J. C. Org. Lett. 2014, 16, 5548.
[54]	Zhang R.; Guo W.; Duan M.; Houk K. N.; Sun J. Angew. Chem., Int. Ed. 2019, 58, 18055.

手性有机硒化合物的催化不对称合成研究进展

Research Progress on Catalytic Asymmetric Synthesis of Chiral Organoselenium Compounds

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 26

References 54

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zhanglong Yu, Zhongliang Li, Changjiang Yang, Qiangshuai Gu, Xinyuan Liu. Research Progress on Copper-Catalyzed Enantioselective Desymmetrization of Diols^★ [J]. Acta Chimica Sinica, 2023, 81(8): 955-966.
[2]	Shuang Yang, Ningyi Wang, Qingqing Hang, Yuchen Zhang, Feng Shi. Advances in Catalytic Asymmetric Reactions Involving o-Hydroxyphenyl Substituted p-Quinone Methides^★ [J]. Acta Chimica Sinica, 2023, 81(7): 793-808.
[3]	Rui-Xiang Wang, Qing-Ru Zhao, Qing Gu, Shu-Li You. Gold/Iridium Catalyzed Alkynylamide Cyclization/Asymmetric Allylic Benzylation Cascade Reaction^★ [J]. Acta Chimica Sinica, 2023, 81(5): 431-434.
[4]	Qingduan Meng, Jiahong Han, Yixiao Pan, Wei Hao, Qing-Hua Fan. Asymmetric Synthesis of C₁-Symmetric Chiral N-Heterocyclic Carbene (NHC) Ligands and Their Applications in Asymmetric Catalysis^★ [J]. Acta Chimica Sinica, 2023, 81(10): 1271-1279.
[5]	Lai Zhang, Jian Xiao, Yawen Wang, Yu Peng. Recent Advances on the Construction of Chiral Dihydrobenzofurans by Asymmetric [3+2] Cyclization Reactions of Phenols (Quinones) and Alkenes [J]. Acta Chimica Sinica, 2022, 80(8): 1152-1164.
[6]	Jinyue Ma, Lufei Huang, Baowen Zhou, Lin Yao. Construction and Catalysis Advances of Inorganic Chiral Nanostructures [J]. Acta Chimica Sinica, 2022, 80(11): 1507-1523.
[7]	Qing-Ru Zhao, Ru Jiang, Shu-Li You. Ir-catalyzed Sequential Asymmetric Allylic Substitution/Olefin Isomerization for the Synthesis of Axially Chiral Compounds [J]. Acta Chimica Sinica, 2021, 79(9): 1107-1112.
[8]	Bo-Shuai Mu, Zhi-Hao Zhang, Wen-Biao Wu, Jin-Sheng Yu, Jian Zhou. Recent Advances in Synthesis of Chiral 1,2-Dihydropyridines [J]. Acta Chimica Sinica, 2021, 79(6): 685-693.
[9]	Yi Li, Ming-Hua Xu. Applications of Asymmetric Petasis Reaction in the Synthesis of Chiral Amines [J]. Acta Chimica Sinica, 2021, 79(11): 1345-1359.
[10]	Wang Qiang, Gu Qing, You Shu-Li. Recent Progress on Transition-Metal-Catalyzed Asymmetric C-H Bond Functionalization for the Synthesis of Biaryl Atropisomers [J]. Acta Chim. Sinica, 2019, 77(8): 690-704.
[11]	Zhou Yuanchun, Zhou Zhi, Du Wei, Chen Yingchun. Asymmetric Inverse-Electron-Demand Diels-Alder Reaction of 2-Pyrone and 2,5-Dienones via HOMO-Activation [J]. Acta Chim. Sinica, 2018, 76(5): 382-386.
[12]	Li Shu-Sen, Wang Jianbo. Recent Advance in Asymmetric Trifluoromethylthiolation [J]. Acta Chim. Sinica, 2018, 76(12): 913-924.
[13]	Lu Hong, Liu Jin-Yu, Li Hong-Yu, Xu Peng-Fei. Recent Developments in N-Heterocyclic Carbene and Transition-Metal Cooperative Catalysis [J]. Acta Chim. Sinica, 2018, 76(11): 831-837.
[14]	Zhou Xiao-Le, Su Yong-Liang, Wang Pu-Sheng, Gong Liu-Zhu. Asymmetric Allylic C-H Alkylation of 1,4-Dienes with Aldehydes [J]. Acta Chim. Sinica, 2018, 76(11): 857-861.
[15]	Li Sujia, Lü Jian, Luo Sanzhong. Enantioselective Indium(I)/Chiral Phosphoric Acid-catalyzed[4+2] Cycloaddition of Simple Olefin and β,γ-Unsaturated α-Keto Esters [J]. Acta Chim. Sinica, 2018, 76(11): 869-873.