氨基酸作为瞬态导向基在碳氢键活化反应中的研究进展

doi:10.6023/cjoc202212012

摘要/Abstract

近年来, 基于瞬态导向策略的碳氢键活化获得了极大关注, 与传统的碳氢键活化反应相比, 瞬态导向基团辅助碳氢键活化无需额外进行导向基的预安装和后期去除步骤, 大大提高了反应的原子和步骤经济性. 在目前发现的瞬态导向基中, 氨基酸作为导向基进行碳氢活化获得了重大成果. 氨基酸具有廉价易得、来源广泛及结构丰富多样的优点, 通过使用α或β-氨基酸进行导向控制碳氢活化反应的位点选择性, 并且可利用氨基酸的固有手性诱导反应的立体选择性. 综述了近年来以氨基酸为瞬态导向基、过渡金属催化的碳氢键活化研究进展, 按照不同氨基酸导向基所进行的各类底物的C—H官能团化反应进行分类, 并对该领域目前的局限和未来发展进行了总结和展望.

关键词: 瞬态导向基团, 氨基酸, 碳氢活化, 过渡金属

In recent years, the transient directing group (TDG)-based strategy of C—H activation has attracted significant attention. Compared with the typical C—H activation reactions, TDG-assisted C—H activation does not require external pre-installation and post-removal steps of directing groups, which significantly improve the atom and step economy. Amino acid-based TDGs for C—H activation have achieved significant successes among the known TDGs. Amino acids have the advantages including low cost, widely existing and diverse structures. The site selectivity of C—H activation can be controlled by using α- or β-amino acids. By using the inherent chirality of amino acids, the stereo-selectivity of reactions can be realized. The research progress of transition-metal-catalyzed C—H bond activation and functionalization with amino acids as TDGs in recent years is summarized, which is classified according to the type of amino acids for C—H activation reactions of various substrates. Finally, the limitations of previous works and perspectives on this cutting-edge area are also described.

Key words: transient directing group, amino acid, C—H activation, transition metal

引用此文

董思凡, 李昊龙, 秦源, 范士明, 刘守信. 氨基酸作为瞬态导向基在碳氢键活化反应中的研究进展[J]. 有机化学, 2023, 43(7): 2351-2367.

Sifan Dong, Haolong Li, Yuan Qin, Shiming Fan, Shouxin Liu. Research Progress of Amino Acids as Transient Directing Groups in C—H Bond Activation Reactions[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2351-2367.

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图/表 40

图式1. 传统导向基和瞬态导向基的导向策略

Scheme 1. Directing strategies for traditional and transient directing groups

图1. 氨基酸导向基

Figure 1. Amino acid directing groups

图式2. 钯催化芳香醛苄位C(sp3)—H键芳基化和脂肪酮的 β-C(sp3)—H键芳基化反应

Scheme 2. Palladium-catalyzed benzylic C(sp3)—H arylation of aromatic aldehydes and β-C(sp3)—H arylation of aliphatic ketones

图式3. 钯催化多环芳烃的合成

Scheme 3. Palladium-catalyzed synthesis of polycyclic aromatic hydrocarbons

图式4. 钯催化芳香酮的邻位C(sp2)—H键芳基化反应

Scheme 4. Palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehydes

图式5. 钯催化芳香酮的邻位C(sp2)—H键芳基化反应机理

Scheme 5. Proposed catalytic mechanism of palladium-catalyzed ortho-C(sp2)—H arylation of aromatic ketones

图式6. 钯催化吲哚和氮杂吲哚的区域选择性C(4)官能团化反应

Scheme 6. Palladium-catalyzed regioselective C(4) functionalization of indole and azaindole

图式7. 钯催化吲哚C(4)位芳基化反应机理

Scheme 7. Proposed catalytic mechanism of palladium-catalyzed arylation of indole at C(4)

图式8. 钯催化芳香醛的邻位C(sp2)—H键芳基化反应

Scheme 8. Palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehydes

图式9. 钯催化芳香醛的邻位C(sp2)—H键芳基化反应

Scheme 9. Palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehydes

图式10. 钯催化芳香醛的邻位C(sp2)—H键芳基化反应机理

Scheme 10. Proposed catalytic mechanism of palladium-catalyzed ortho-C(sp2)—H arylation of aromatic aldehyde

图式11. 钯催化脂肪醛β-C(sp3)—H键芳基化反应

Scheme 11. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

图式12. 钯催化芳香醛苄位C(sp3)—H键芳基化反应

Scheme 12. Palladium-catalyzed benzylic C(sp3)—H arylation of aromatic aldehydes

图式13. 钯催化脂肪醛β-C(sp3)—H芳基化反应

Scheme 13. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

图式14. 钯催化脂肪醛γ-C(sp3)—H芳基化反应

Scheme 14. Palladium-catalyzed γ-C(sp3)—H arylation of aliphatic aldehydes

图式15. 钯催化烯烃苯甲醛C(alkenyl)—H烯基化反应

Scheme 15. Palladium-catalyzed olefin benzaldehyde C(alkenyl)—H alkenylation

图式16. 钯催化C(alkenyl)—H烯基化机理

Scheme 16. Proposed catalytic mechanism of palladium-catalyzed C(alkenyl)—H alkenylation

图式17. 钯催化芳香醛C(sp2)—H氘化反应

Scheme 17. Palladium-catalyzed C(sp2)—H deuteration of aromatic aldehydes

图式18. 钯催化芳香醛C(sp2)—H氘化反应机理

Scheme 18. Proposed catalytic mechanism of palladium-catalyzed C(sp2)—H deuteration of aromatic aldehydes

图2. [6,5]和[5,6]-双环钯中间体

Figure 2. [6,5] and [5,6]-bicyclic palladium intermediates

图式19. 钯催化脂肪醛β-C(sp3)—H芳基化反应

Scheme 19. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

图式20. 钯催化脂肪醛β-C(sp3)—H芳基化反应的循环

Scheme 20. Proposed catalytic cycle of palladium-catalyzed β-C(sp3)—H arylation of aliphatic aldehydes

图式21. 钯催化饱和醛的β-C—H键芳基化反应

Scheme 21. Palladium-catalyzed β-C—H arylation of saturated aldehydes

图式22. 钯催化饱和醛的β-C—H键芳基化芳基化反应的循环机理

Scheme 22. Proposed catalytic cycle of palladium-catalyzed β-C—H arylation of saturated aldehydes

图式23. 铑催化芳香醛分子内烯烃化反应

Scheme 23. Rhodium(III)-catalyzed intramolecular olefin hydroarylation of aromatic aldehydes

图式24. 铑催化芳香醛分子内烯烃化反应的循环机理

Scheme 24. Proposed catalytic cycle of rhodium(III)-catalyzed intramolecular olefin hydroarylation of aromatic aldehydes

图式25. 酮催化芳香醛邻位C(sp2)—H磺酰化反应

Scheme 25. Ketone-catalyzed ortho-C(sp2)—H sulfonylation of aromatic aldehydes

图式26. 酮催化芳香醛邻位C(sp2)—H磺酰化反应的循环

Scheme 26. Proposed catalytic cycle of ketone-catalyzed ortho-C(sp2)—H sulfonylation of aromatic aldehydes

图式27. 钯催化脂肪酮的β-C(sp3)—H芳基化反应

Scheme 27. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic ketones

图式28. 钯催化苯甲醛和芳基碘合成芴酮

Scheme 28. Palladium-catalyzed synthesis of fluorenones from benzaldehydes and aryl iodides

图式29. 钯催化苯甲醛和芳基碘合成芴酮循环

Scheme 29. Proposed catalytic cycle of palladium-catalyzed synthesis of fluorenones from benzaldehydes and aryl iodides

图3. [5,5]或[5,6]-双环钯中间体

Figure 3. [5,5] or [5,6]-bicyclic palladium intermediate

图式30. 钯催化芳基醛苄位C(sp3)—H键芳基化反应

Scheme 30. Palladium-catalyzed benzylic C(sp3)—H arylation of aromatic aldehydes

图式31. 钯催化芳香醛苄位C(sp3)—H键氟化反应

Scheme 31. Palladium-catalyzed benzylic C(sp3)—H fluoridation of aromatic aldehydes

图式32. 钯催化阻转选择性C(sp2)—H键烯基化反应

Scheme 32. Palladium-catalyzed atroposelective C(sp2)—H olefination of biaryl aldehydes

图式33. 钯催化联芳醛类阻转选择性C(sp2)—H键炔基化反应

Scheme 33. Palladium-catalyzed atroposelective C(sp2)—H alkynylation of biaryl aldehydes

图式34. 钯催化酰基二茂铁的不对称C(sp2)—H键芳基化反应

Scheme 34. Palladium-catalyzed enantioselective C(sp2)—H arylation of ferrocenyl ketones

图式35. 钯催化阻转选择性C(sp2)—H键芳基化反应

Scheme 35. Palladium-catalyzed atroposelective C(sp2)—H arylation of biaryl aldehydes

图式36. 钯催化烯烃苯甲醛不对称还原Heck氢芳基化及机理

Scheme 36. Palladium-catalyzed asymmetric reductive Heck arylation of alkenyl benzaldehydes and proposed mechanism

图式37. 钯催化脂肪酮的β-C(sp3)—H芳基化反应

Scheme 37. Palladium-catalyzed β-C(sp3)—H arylation of aliphatic ketones

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