钯催化共轭二烯的不对称氢官能团化

doi:10.6023/cjoc202302010

摘要/Abstract

由于原料来源广泛、高原子经济性和高立体选择性控制等优势, 钯催化共轭二烯的不对称氢官能团化已发展成为一种高效合成手性烯丙基片段的方法, 包括构建烯丙基C—C、C—N、C—S、C—P、C—Si和C—O键等. 总结了近几十年来该领域的发展现状、最新进展以及机制特点等. 根据所构建的化学键的不同, 主要涵盖了不对称氢烷基化、氢胺化、氢膦化、氢砜化、氢硅化和氢醚化六个部分.

关键词: 钯催化, 共轭二烯, 氢官能团化, 不对称合成

Because of the broad substrate availability, high atom economy and efficient stereocontrol, palladium-catalzyed asymmetric hydrofunctionalizations of conjugated dienes have emerged as an efficient route to construct enantioenriched allylic motifs, including allylic C—C, C—N, C—S, C—P, C—Si and C—O bonds. The development, advance and mechanistic features of this area in the past decades are summarized. Based on the types of allylic stereogenic centers constructed via this strategy, the review is divided into six parts, including asymmetric hydroalkylation, hydroamination, hydrophosphinylation, hydrosulfonylation, hydrosilylation and hydroalkoxylation.

Key words: palladium catalysis, conjugated dienes, hydrofunctionalization, asymmetric synthesis

引用此文

王玉超, 刘晋彪, 何智涛. 钯催化共轭二烯的不对称氢官能团化[J]. 有机化学, 2023, 43(8): 2614-2627.

Yuchao Wang, Jinbiao Liu, Zhitao He. Palladium-Catalyzed Asymmetric Hydrofunctionalizations of Conjugated Dienes[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2614-2627.

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图/表 30

图式1. 钯催化共轭二烯的不对称氢官能团化的机理特点

Scheme 1. Mechanistic characters for palladium-catalyzed asymmetric hydrofunctionalizations of conjugated dienes

图式2. 首次的共轭二烯的不对称氢烷基化反应

Scheme 2. The first enantioselective hydroalkylation of 1,3- dienes

图式3. Pd-PHOX催化共轭二烯的不对称氢烷基化反应

Scheme 3. Pd-PHOX-catalyzed asymmetric hydroalkylation of conjugated dienes

图式4. 非末端二烯的不对称氢烷基化反应

Scheme 4. Asymmetric hydroalkylation of non-terminal dienes

图式5. 内二烯的不对称氢官能团化反应机理

Scheme 5. Plausible mechanism for asymmetric hydroalkylation of internal dienes

图式6. 季碳手性中心的构建

Scheme 6. The construction of quaternary stereogenic centers

图式7. 共轭二烯与吖内酯的不对称氢烷基化反应

Scheme 7. Asymmetric hydroalkylation of conjugated dienes with azlactones

图式8. Pd(OAc)2催化共轭二烯与吖内酯的氢烷基化反应

Scheme 8. Pd(OAc)2 catalyzed asymmetric hydroalkylation of 1,3-dienes with azlactones

图式9. 立体选择性合成高烯丙基α-三氟甲基胺

Scheme 9. Stereoselective synthesis of homoallylic α?trifluoro- methyl amines

图式10. 钯/铜协同催化共轭二烯与醛亚胺酯的立体发散性氢烷基化反应

Scheme 10. Pd/Cu-catalyzed stereodivergent hydroalkylation of conjugated dienes with aldimine esters

图式11. 钯和胺协同催化共轭二烯与醛的立体发散性氢烷基化反应

Scheme 11. Synergistic Pd/amine-catalyzed stereodivergent hy- droalkylation of conjugated dienes with aldehydes

图式12. 钯和路易斯碱协同催化共轭二烯与乙酸五氟苯酯的立体发散性氢烷基化反应

Scheme 12. Synergistic Pd/Lewis base-catalyzed stereodivergent hydroalkylation of conjugated dienes with pentafluorophenyl acetates

图式13. 钯和相转移催化剂协同催化共轭二烯的立体发散性氢烷基化反应

Scheme 13. Synergistic palladium/PTC-catalyzed stereodivergent hydroalkylation of conjugated dienes

图式14. 钯氢催化极性反转的不对称1,5-共轭加成反应

Scheme 14. Umpolung asymmetric 1,5-conjugate additions via palladium hydride catalysis

图式15. 首例共轭二烯与芳胺的不对称氢胺化反应

Scheme 15. The first asymmetric hydroamination of conjugated dienes with aromatic amines

图式16. 开链共轭二烯与脂肪胺的不对称氢胺化反应

Scheme 16. Asymmetric hydroamination of linear conjugated dienes with aliphatic amines

图式17. 内部二烯与胺的不对称氢胺化反应

Scheme 17. Asymmetric hydroamination of internal dienes with amines

图式18. 内烯的氢胺化反应机理

Scheme 18. Proposed mechanism for hydroamination of internal dienes

图式19. 共轭二烯与吡唑的不对称氢胺化反应

Scheme 19. Asymmetric hydroamination of conjugated dienes with pyrazoles

图式20. 共轭二烯与二苯氧膦的不对称氢膦化反应

Scheme 20. Asymmetric hydrophosphinylation of conjugated dienes with phosphine oxides

图式21. 共轭二烯与磺酸的不对称氢砜化反应

Scheme 21. Asymmetric hydrosulfonylation of conjugated dienes with sulfinic acids

图式22. 共轭二烯与磺酰肼的不对称氢砜化反应

Scheme 22. Asymmetric hydrosulfonylation of conjugated dienes with sulfonyl hydrazides

图式23. 不对称氢砜化反应机理

Scheme 23. Proposed mechanism for asymmetric hydrosulfonylation

图式24. 首例环戊二烯的不对称氢硅化反应

Scheme 24. The first asymmetric hydrosilylation of cyclopentadiene

图式25. 环戊二烯和环己二烯的不对称氢硅化反应

Scheme 25. Asymmetric hydrosilylation of cyclopentadiene and cyclohexadiene

图式26. Hayashi课题组关于环状二烯的不对称氢硅化反应研究

Scheme 26. Asymmetric hydrosilylation of cyclic dienes in Hayashi group

图式27. 线性二烯的不对称氢硅化反应

Scheme 27. Asymmetric hydrosilylation of linear dienes

图式28. 钯催化共轭二烯的不对称氢烷氧基化反应

Scheme 28. Pd-catalyzed asymmetric hydroalkoxylation of conjugated dienes

图式29. 不对称氢烷氧基化反应的可能机理

Scheme 29. Proposed mechanism for asymmetric hydroalkoxylation

图式30. 钯催化共轭二烯的不对称水合反应和氢胺羟化反应

Scheme 30. Pd-catalyzed asymmetric hydration and hydroaminoxylation of conjugated dienes

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