钯和手性磷酸协同催化高效构建手性分子的研究进展

doi:10.6023/cjoc202211043

摘要/Abstract

过渡金属钯催化不对称反应是高效合成手性化合物的重要途径之一, 在过去几十年里, 发展迅速并取得了巨大的进展, 但有些反应仅使用钯催化体系难以获得高的反应活性和优异的立体选择性. 将过渡金属钯催化体系和有机小分子催化体系联合起来有利于解决单一催化剂面临的难点问题, 是合成化学的研究热点之一, 备受人们的青睐. 近些年, 运用过渡金属钯和手性磷酸的协同催化体系, 高效地实现了一系列不对称催化反应, 良好地控制了化学选择性、区域选择性和立体选择性, 已经取得了一些可观的研究成果和重要的突破. 简要综述了运用该协同催化体系实现不对称烯丙基化反应、C(sp³)—H键官能团化反应、C(sp²)—H键官能团化反应以及一些其它类型不对称催化反应的研究现状, 系统地分析了催化剂与底物之间的相互作用机制, 深入地讨论了影响反应活性和选择性的因素.

关键词: 协同催化, 钯催化, 手性磷酸, 手性化合物, 立体选择性

Transition metal palladium-catalyzed asymmetric reaction is an important and efficient method to synthesize chiral compounds. It has made considerable progress and achieved great success in the past decades. However, some reactions could not achieve high reactivity and excellent stereoselectivity just promoted by transition metal palladium catalysis. Therefore, it is of great significance to combine transition metal palladium catalysis and organocatalysis, which could be conducive to dissolve these challenging problems and received great attention. In recent years, a variety of asymmetric catalytic reactions have been efficiently realized by the synergistic catalysis system of transition metal palladium catalysis and chiral phosphoric acids with high chemo-, regio-, and stereoselectivity, and considerable research results and some important breakthroughs have been achieved. The recent progress of asymmetric allylation reaction, C(sp³)—H, C(sp²)—H functionalization and other reactions promoted by this synergistic catalysis system is summarized, the interaction between catalysts and substrates is systematically analyzed, and the influence factors of reactivity and selectivity are deeply discussed.

Key words: synergistic catalysis, Pd catalysis, chiral phosphoric acid, chiral compound, stereoselectivity

引用此文

向勋, 何照林, 董秀琴. 钯和手性磷酸协同催化高效构建手性分子的研究进展[J]. 有机化学, 2023, 43(3): 791-808.

Xun Xiang, Zhaolin He, Xiuqin Dong. Recent Advances of Efficient Synthesis of Chiral Molecules Promoted by Pd/Chiral Phosphoric Acid Synergistic Catalysis[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 791-808.

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图/表 38

图式1. 钯/手性磷酸协同催化α-支链醛的对映选择性烯丙基烷基化反应

Scheme 1. Pd/chiral phosphoric acid-catalyzed enantioselective α-allylic alkylation of α-branched aldehydes

图式2. α-支链醛的对映选择性烯丙基烷基化反应的可能机理

Scheme 2. Possible mechanism of enantioselective α-allylic alkylation of α-branched aldehydes

图式3. 醛与简单烯丙醇的对映选择性烯丙基化反应

Scheme 3. Asymmetric α-allylation of aldehydes with simple allylic alcohols

图式4. 钯/手性磷酸催化吡唑-5-酮的不对称烯丙基化反应

Scheme 4. Pd/chiral phosphoric acid catalyzed asymmetric allylic alkylation of pyrazol-5-ones

图式5. 吡唑-5-酮不对称烯丙基化反应的可能催化循环

Scheme 5. Proposed catalytic cycle for the asymmetric allylic alkylation of pyrazol-5-ones

图式6. 外消旋烯丙醇的对映选择性胺化反应

Scheme 6. Enantioselective amination of racemic allylic alcohols

图式7. 酮α位对映选择性烯丙基化反应

Scheme 7. Enantioselective α-allylation of ketones

图式8. 不对称酮α位对映选择性烯丙基化的可能机理

Scheme 8. Possible mechanism of asymmetric ketone enantioselective α-allylation

图式9. 三元催化的三组分不对称烯丙基化反应

Scheme 9. Ternary catalysis enabled three-component asymmetric allylic alkylation reaction

图式10. 钯/手性磷酸催化对映选择性烯丙基C—H键活化合成手性螺环分子

Scheme 10. Pd/chiral phosphoric acid-catalyzed asymmetric allylic C—H activation to access chiral spirocyclic rings

图式11. 钯催化8-氨基喹啉酰胺的仲β-C(sp3)—H键的不对称芳基化反应

Scheme 11. Pd-catalyzed asymmetric arylation of secondary β-C(sp3)—H bonds of 8-aminoquinoline amides

图式12. 钯催化C—H键氧化硼化实现简单烯烃的立体选择性羰基烯丙基化反应

Scheme 12. Stereoselective carbonyl allylation with simple olefins promoted by Pd-catalyzed C—H oxidative borylation

图式13. 钯/手性磷酸协同催化端烯与吡唑-5-酮的不对称烯丙基C—H键烷基化反应

Scheme 13. Asymmetric allylic C—H alkylation of terminal olefins with pyrazol-5-ones through cooperative catalysis of palladium complex and CAP

图式14. 取代1,4-戊二烯与吡唑-5-酮的不对称烯丙基C—H键烷基化反应及其在合成中的应用

Scheme 14. Allylic C—H alkylation of substituted 1,4-pentadienes with pyrazol-5-ones and its synthetic application

图式15. 钯催化不对称胺的苄基C—H键芳基化反应

Scheme 15. Pd-catalyzed asymmetric benzylic C—H arylation of amines

图式16. 钯催化对映体选择性C—H键胺化反应

Scheme 16. Enantioselective Pd(II)-catalyzed C—H amination reaction

图式17. 钯催化的不对称C(sp3)—H键芳基化反应

Scheme 17. Pd-catalyzed asymmetric C(sp3)—H arylation reaction

图式18. 硫代酰胺的对映选择性α位C—H键芳基化反应

Scheme 18. Enantioselective α-C—H arylation of thioamides

图式19. 钯催化1,4-二烯和醛的烯丙基C—H键不对称烷基化反应

Scheme 19. Pd-catalyzed asymmetric allylic C—H alkylation of 1,4-dienes with aldehydes

图式20. 钯催化亚甲基C(sp3)—H键的对映选择性芳基化反应

Scheme 20. Pd-catalyzed enantioselective arylation of methylene C(sp3)—H bonds

图式21. 硫代酰胺的对映选择性β位C—H键官能化

Scheme 21. Enantioselective β-C—H functionalization of thioamides

图式22. C(sp3)—H键的对映选择性分子内芳基化反应

Scheme 22. Enantioselective intramolecular arylation of C(sp3)—H bonds

图式23. 钯催化不对称C—H键芳基化反应合成平面手性二茂铁分子

Scheme 23. Pd-catalyzed asymmetric C—H arylation for the synthesis of planar chiral ferrocenes

图式24. 钯催化不对称C—H键活化合成含P-手性中心的二苯并磷类化合物

Scheme 24. Pd-catalyzed asymmetric C—H bond activation for the synthesis of P?stereogenic dibenzophospholes

图式25. 钯催化不对称C—H键烯基化反应合成联芳基轴手性化合物

Scheme 25. Enantioselective synthesis of biaryl atropisomers by Pd-catalyzed C—H olefination

图式26. 钯催化不对称C—H键烯丙基化反应合成轴手性联芳基-2-胺类化合物

Scheme 26. Synthesis of axially chiral biaryl-2-amines via Pd-catalyzed asymmetric C—H allylation

图式27. 钯催化不对称C—H键烯基化反应合成轴手性联芳基-2-胺类化合物

Scheme 27. Synthesis of axially chiral biaryl-2-amines via Pd-catalyzed asymmetric C—H olefination

图式28. 钯催化烯烃C—H键烯基化反应合成含轴手性的共轭双烯化合物

Scheme 28. Atroposelective synthesis of conjugated diene-based axially chiral styrenes via Pd-catalyzed alkenyl C—H olefination

图式29. 钯催化的选择性C—H键烯基化反应和烯丙基化反应

Scheme 29. Pd-catalyzed atroposelective C—H olefination and allylation reaction

图式30. 双轴手性联苯化合物的合成

Scheme 30. Synthesis of diaxially chiral biaryls

图式31. 基于Oxa-Diels-Alder环加成的串联环化反应

Scheme 31. Asymmetric cascade annulation based on oxa- Diels-Alder cycloaddition

图式32. 烯烃的对映选择性芳基硼化反应

Scheme 32. Enantioselective aryl borylation of alkene

图式33. 烯烃的芳基硼化反应的可能机理

Scheme 33. Possible mechanism of enantioselective aryl boration of alkenes

图式34. 对映选择性丙烯酸苄酯的双芳基化反应

Scheme 34. Enantioselective diarylation of benzyl acrylate

图式35. 环状烯烃和芳基重氮盐的不对称Heck-Matsuda芳基化反应

Scheme 35. Asymmetric Heck-Matsuda arylation of cyclic alkenes and aryl diazonium salts

图式36. 钯催化环状烯烃和芳基重氮盐的不对称Heck- Matsuda芳基化反应的可能机理

Scheme 36. Possible mechanism of Pd-catalyzed asymmetric Heck- Matsuda arylation of cyclic alkenes and aryl diazonium salts

图式37. 螺环烯烃和芳基重氮盐的不对称Heck-Matsuda芳基化反应

Scheme 37. Asymmetric Heck-Matsuda arylation of spirocyclic alkenes and aryl diazonium salts

图式38. 钯催化azlactones和非共轭烯烃的不对称α位烷基化反应

Scheme 38. Pd-catalyzed asymmetric α-alkylation of azlactones with nonconjugated alkenes

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