手性有机硒化合物的催化不对称合成研究进展

doi:10.6023/A25080280

摘要/Abstract

手性有机硒化合物在合成化学、材料科学、医药和农药等领域具有广泛的应用, 在不对称催化领域还可以用作手性配体或有机小分子催化剂. 因此, 手性有机硒化合物的不对称合成受到化学家们的重视. 利用含硒试剂与相应底物的催化不对称C—Se偶联反应是合成有机硒化合物最直接且最有效的策略之一. 此综述着重介绍了利用该策略构建手性有机硒化合物的研究进展. 根据不同的硒源类型, 将反应分为亲电有机硒试剂与亲核底物的不对称偶联反应和亲核有机硒试剂与亲电底物的不对称偶联反应两类. 另外, 对一些代表性反应的机理和底物适用范围做了简要介绍.

关键词: 手性有机硒化合物, 不对称催化, 亲电硒试剂, 亲核硒试剂, C—Se键构建

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

引用此文

李晖, 殷亮. 手性有机硒化合物的催化不对称合成研究进展[J]. 化学学报, 2025, 83(10): 1237-1251.

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

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图/表 26

图1. 代表性亲电硒化试剂和亲核硒化试剂

Figure 1. Representative electrophilic and nucleophilic selenization reagents

图式1. 以亲电有机硒试剂为硒源的手性有机硒化合物不对称催化合成方法

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

图式2. 超分子催化的不对称去对称化硒化环醚化反应

Scheme 2. Desymmetrizing asymmetric selenoetherification through supramolecular catalysis

图式3. C2轴对称硫基催化剂催化的对映选择性硒化内酯化反应

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

图式4. 1,1-二取代烯烃的硒化-环化反应构建4H-3,1-苯并噁嗪

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

图式5. α,β-不饱和酮的对映选择性硒化磺酰化反应

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

图式6. 烯醇和联烯基醇的不对称硒基化-半频哪醇重排反应

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

图式7. 铑催化的1-芳基异喹啉的阻转选择性硒基化反应

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

图式8. 含羰基的氮氧杂环化合物的对映选择性α-硒基化反应

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

图式9. 镍催化的β-酮酸酯的对映选择性α-硒氰化反应

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

图式10. 一价铜催化的2-酰基咪唑的对映选择性α-硒基化反应

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

图式11. 一价铜催化的对映选择性插烯硒基化反应

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

图式12. 烷亚基β-酮酸酯的不对称分子内氧杂Michael加成-硒氰化串联反应

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

图式13. 二价铑/手性胍协同催化的Se—S键的不对称卡宾插入反应

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

图式14. 以亲核有机硒试剂为硒源的手性有机硒化合物的不对称催化合成方法

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

图式15. 铑催化的杂双环烯烃的对映选择性氢硒化反应

Scheme 15. Rhodium-catalyzed enantioselective hydroselenation of heterobicyclic alkenes

图式16. 铑催化的苯乙烯类化合物的对映选择性氢硒化反应

Scheme 16. Rhodium-catalyzed enantioselective hydroselenation of styrenes

图式17. 铑催化的环丙烯的对映选择性氢硒化反应

Scheme 17. Rhodium-catalyzed enantioselective hydroselenation of cyclopropenes

图式18. 铑催化的1-炔基吲哚的阻转选择性氢硒化反应

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

图式19. 有机小分子催化的1-炔基萘-2-酚的阻转选择性氢硒化反应

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

图式20. 手性有机小分子催化的硒醇与酮亚胺的不对称加成反应

Scheme 20. Organocatalytic asymmetric addition of selenol to ketimine

图式21. 手性氮杂环卡宾催化的硒醇与α,β-不饱和羰基化合物的不对称Michael加成反应

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

图式22. 一价铜催化的硒醇或硒酚与α,β-不饱和硫代酰胺的不对称共轭加成反应

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

图式23. 卡宾催化的硒代酰胺与溴代烯醛的立体选择性[3＋3]环化反应

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

图式24. 二价钴催化的烯丙基硒化合物与α-重氮吡唑酰胺的不对称[2,3]-σ迁移反应

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

图式25. 手性布朗斯特酸催化的氧杂环丁烷的不对称去对称化分子内开环反应

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

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