铜催化的手性膦化合物不对称合成研究进展

doi:10.6023/cjoc202405002

摘要/Abstract

手性含磷有机化合物在医药、农药、功能材料等领域具有广泛的应用, 还可用作不对称催化中的手性配体和有机小分子催化剂. 因此, 手性膦化合物的不对称合成受到合成化学家们的重视. 利用P—H化合物立体选择性地构建 P—C键和P—N键等是合成手性膦化合物最直接且最有效的方法之一. 着重介绍了铜在手性配体或手性有机小分子催化剂参与下高效构建手性膦化合物方面的研究进展. 根据铜催化剂在反应过程中价态是否发生改变, 将反应分为变价催化反应和非变价催化反应, 反应生成了P-手性、碳骨架手性或兼具P-手性和碳骨架手性的膦化合物. 同时, 对一些代表性的反应机理和产物应用也做了介绍.

关键词: 铜催化, 不对称催化, 手性膦化合物, P-手性

Chiral organophosphorus compounds have a wide range of application in the fields of medicine, pesticides, and functional materials, and also serve as versatile ligands or organocatalysts in asymmetric catalysis. Therefore, their asymmetric synthesis has attracted an increasing attention from chemists and has become one hot research topic in recent years. Asymmetric P—C or P—N bond formation by using organophosphorus compounds bearing P—H bond and various electrophilic partners serves as a straightforward and powerful strategy for constructing chiral organophosphorus compounds. The recent progress in asymmetric synthesis of chiral organophosphorus compounds catalyzed by chiral copper complexes or copper/organocatalyst co-catalytic systems is summarized. P-Chiral or/and backbone chiral organophosphorus compounds were obtained in these reactions. This paper is divided into two sections based on whether the valence state of copper is changed or not during the reaction process. Aside from the substrate scopes, the mechanisms and potential applications of some representative methodologies are also included.

Key words: copper catalysis, asymmetric synthesis, chiral organophosphorus compounds, P-chirality

引用此文

李晖, 殷亮. 铜催化的手性膦化合物不对称合成研究进展[J]. 有机化学, 2024, 44(12): 3575-3586.

Hui Li, Liang Yin. Research Progress on Copper-Catalyzed Asymmetric Synthesis of Chiral Organophosphorus Compounds[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3575-3586.

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图/表 18

图式1. 二级膦或其氧化物与亲电试剂的立体选择性反应

Scheme 1. Stereoselective reaction of secondary phosphines or their oxides with electrophiles

图式2. 由二级膦生成的金属-膦物种的差向异构

Scheme 2. Epimerization of metal-phosphido species derived from secondary phosphines

图式3. 二级膦氧化物的互变异构

Scheme 3. Tautomerization of secondary phosphine oxides

图式4. 铜催化剂的价态变化

Scheme 4. Valence state change of copper catalysts

图式5. N-杂环卡宾铜催化的α,β-不饱和酮的不对称氢膦化反应

Scheme 5. N-Heterocyclic carbene-copper-catalyzed asymmetric hydrophosphination of α,β-unsaturated ketones

图式6. 铜催化的α,β-不饱和酰胺的不对称氢膦化反应

Scheme 6. Copper-catalyzed asymmetric hydrophosphination of α,β-unsaturated amides

图式7. 铜催化的α,β-不饱和酰酯的不对称氢膦化反应

Scheme 7. Copper-catalyzed asymmetric hydrophosphination of α,β-unsaturated esters

图式8. 铜催化的α,β-不饱和膦硫化物的不对称氢膦化反应

Scheme 8. Copper-catalyzed asymmetric hydrophosphination of α,β-unsaturated phosphine sulfides

图式9. 铜催化的1-乙烯基喹啉衍生物的不对称氢膦化反应

Scheme 9. Copper-catalyzed asymmetric hydrophosphination of alkenyl isoquinolines

图式10. 铜催化的3,3-二取代环丙烯的不对称氢膦化反应

Scheme 10. Copper-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes

图式11. 3,3-二取代环丙烯不对称氢膦化反应机理

Scheme 11. Mechanism of asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes

图式12. 铜和CPA协同催化的1-炔基萘-2-酚的不对称氢膦酰化反应

Scheme 12. Copper and CPA co-catalyzed asymmetric hydrophosphinylation of 1-ethynylnaphthalen-2-ols

图式13. 铜催化的外消旋二芳基膦的不对称烷基化反应

Scheme 13. Copper-catalyzed asymmetric alkylation of unsymmetrical diarylphosphines

图式14. 铜催化的二级膦氧化物与二芳基碘鎓盐的不对称芳基化反应

Scheme 14. Copper-catalyzed asymmetric arylation of secondary phosphine oxides with diaryliodonium salts

图式15. 铜催化的不对称分子内C-P交叉偶联/环化反应

Scheme 15. Copper-catalyzed asymmetric intramolecular C-P cross-coupling/cyclization

图式16. 铜催化的二级膦氧化物与芳香碘化物的不对称交叉偶联反应

Scheme 16. Copper-catalyzed asymmetric cross-coupling of secondary phosphine oxides and aromatic iodides

图式17. 铜催化的不对称Michaelis-Becker交叉偶联反应

Scheme 17. Copper-catalyzed asymmetric Michaelis-Becker- type cross-coupling reaction

图式18. 铜催化的外消旋二芳基膦的不对称胺基化反应

Scheme 18. Copper-catalyzed asymmetric amination of unsymmetrical diarylphosphines

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