2-取代的3H-吲哚-3-酮类化合物参与的C2位手性吲哚啉-3-酮类化合物的不对称合成研究进展

doi:10.6023/cjoc202407039

摘要/Abstract

含有2,2-二取代吲哚啉-3-酮类骨架的化合物在天然产物、手性药物等诸多领域有着广泛应用. 通过不对称催化高效构建2,2-二取代吲哚啉-3--酮类化合物受到越来越广泛的关注. 综述了近些年国内外在以2-取代的3H-吲哚-3-酮类化合物为底物的不对称催化合成2,2-二取代吲哚啉-3-酮类化合物方面取得的研究进展, 主要从不对称aza- Friedel-Crafts反应、Mannich反应、aza-Diels-Alder反应、aza-Henry反应、aza-Morita-Baylis-Hillman反应以及其他反应等方面进行讨论, 为今后不对称合成C2季碳中心吲哚啉-3-酮类化合物研究提供参考.

关键词: 2-芳基-3H-吲哚-3-酮, 不对称催化, C2季碳中心吲哚啉-3-酮

Compounds containing 2,2-disubstituted indoline-3-one skeletons are widely used in many fields such as natural products and chiral drugs. The efficient construction of 2,2-disubstituted indolin-3-ones by asymmetric catalysis has attracted more and more attention. The research progress in the asymmetric synthesis of 2,2-disubstituted indolin-3-ones using 2-sub- stituted indolin-3-ones as substrates in recent years is reviewed, including asymmetric aza-Friedel-Crafts reaction, Mannich reaction, aza-Diels-Alder reaction, aza-Henry reaction, aza-Morita-Baylis-Hillman reaction and other reactions. It provides a reference for the future asymmetric synthesis of C2 quaternary carbon center indolin-3-one compounds.

Key words: 2-aryl-3H-indol-3-ones, asymmetric catalysis, C2-quaternary indolin-3-ones

引用此文

乔秀秀, 李倩, 赵世娜, 魏瑞琪, 马桃, 何永辉, 赵晓静. 2-取代的3H-吲哚-3-酮类化合物参与的C2位手性吲哚啉-3-酮类化合物的不对称合成研究进展[J]. 有机化学, 2025, 45(4): 1166-1177.

Xiu-Xiu Qiao, Qian Li, Shi'na Zhao, Ruiqi Wei, Tao Ma, Yong-Hui He, Xiao-Jing Zhao. Research Progress in Asymmetric Synthesis of C2 Chiral Indolin-3-ones Involving 2-Substituted-3H-indol-3-ones[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1166-1177.

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图/表 24

图1. 含C2手性季碳吲哚啉-3-酮结构的天然产物分子

Figure 1. Natural product molecules containing C2 chiral quaternary carbon indoline-3-one structure

图式1. 螺环吲哚啉-3-酮和吲哚的不对称aza-Friedel-Crafts反应

Scheme 1. Asymmetric aza-Friedel-Crafts reaction of spiroindolin-3-ones with indoles

图式2. 2-芳基-3H-吲哚-3-酮和吲哚的不对称aza-Friedel- Crafts反应

Scheme 2. Asymmetric aza-Friedel-Crafts reaction of 2-aryl- 3H-indole-3-ones and indoles

图式3. 2-芳基-3H-吲哚-3-酮和吡咯的不对称aza-Friedel- Crafts反应

Scheme 3. Asymmetric aza-Friedel-Crafts reaction of 2-aryl- 3H-indol-3-ones with pyrroles

图式4. 吲哚啉-3-酮-2-羧酸酯与吲哚的不对称aza-Friedel- Crafts反应

Scheme 4. Asymmetric aza-Friedel-Crafts reaction of indole- 3-one-2-carboxylate with indole

图式5. 2-芳基-3H-吲哚-3-酮和萘酚的不对称aza-Friedel- Crafts反应

Scheme 5. Asymmetric aza-Friedel-Crafts reaction of 2-aryl- 3H-indol-3-ones with naphthols

图式6. 2-芳基-3H-吲哚-3-酮和5-氨基吡唑的不对称aza- Friedel-Crafts反应

Scheme 6. Asymmetric aza-Friedel-Crafts reaction of 2-aryl- 3H-indol-3-ones with 5-aminopyrazoles

图式7. 2-芳基-3H-吲哚-3-酮与1-和2-萘酚的不对称aza-Friedel-Crafts反应

Scheme 7. Asymmetric aza-Friedel-Crafts reactions of 2-aryl-3H-indol-3-ones with 1- and 2-naphthol

图式8. L-脯氨酸催化的3H-吲哚-3-酮和醛酮的不对称Mannich反应

Scheme 8. L-Proline-catalyzed asymmetric Mannich reaction of 3H-indole-3-ones with aldehydes and ketones

图式9. 2-芳基-3H-吲哚-3-酮和简单醛酮的不对称Mannich反应

Scheme 9. Asymmetric Mannich reaction of 2-aryl-3H-indol- 3-ones with simple aldehydes and ketones

图式10. 手性磷酸催化构建二氟烷基化吲哚啉-3-酮

Scheme 10. Construction of difluoroalkylated indolin-3-ones by chiral phosphoric acid catalysis

图式11. 2-芳基-3H-吲哚-3-酮和苯乙酮的不对称Mannich反应

Scheme 11. Asymmetric Mannich reaction of 2-aryl-3H-indol- 3-ones with acetophenones

图式12. 新型催化剂催化的吲哚-3-酮类化合物与醛、酮的不对称Mannich反应

Scheme 12. Asymmetric Mannich reaction of indole-3-ones with aldehydes and ketones catalyzed by new catalysts

图式13. Br?nsted酸催化2-芳基-3H-吲哚-3-酮与环戊二烯的不对称aza-Diels-Alder反应

Scheme 13. Asymmetric aza-Diels-Alder reaction of 2-aryl-3H- indol-3-ones with cyclopentadiene catalyzed by Br?nsted acid

图式14. 2-芳基-3H-吲哚-3-酮与2,4-二烯醛的不对称aza- Diels-Alder反应

Scheme 14. Asymmetric aza-Diels-Alder reaction of 2-aryl- 3H-indol-3-ones with 2,4-dienals

图式15. 脯氨酸催化2-芳基-3H-吲哚-3-酮与环烯酮的不对称aza-Diels-Alder反应

Scheme 15. Proline-catalyzed asymmetric aza-Diels-Alder reaction of 2-aryl-3H-indol-3-ones with cyclic ketenes

图式16. 2-芳基-3H-吲哚-3-酮类化合物与未活化二烯的对映选择性aza-Diels-Alder反应

Scheme 16. Enantioselective aza-Diels-Alder reaction of 2-aryl- 3H-indol-3-ones with unactivated diene

图式17. B(C6F5)3和手性磷酸协同催化吲哚-3-酮和α-甲基苯乙烯的不对称酮亚胺-ene反应

Scheme 17. B(C6F5)3 and chiral phosphoric acid synergistically catalyzed the asymmetric ketimine-ene reaction of indole-3-ones and α-methylstyrenes

图式18. 通过金属与Br?nsted酸协同催化构筑C2位季碳立体中心的炔基吲哚啉-3-酮

Scheme 18. Synergistic catalysis of metal and Br?nsted acid to construct alkynylindolin-3-ones with quaternary carbon stereocenters at C2 position

图式19. 2-芳基-3H-吲哚-3-酮和硝基烷烃的不对称氮杂Henry反应

Scheme 19. Asymmetric aza-Henry reaction of 2-aryl-3H-indol- 3-ones with nitroalkanes

图式20. 手性硫脲催化的2-芳基-3H-吲哚-3-酮和α,β-不饱和γ-丁内酰胺的不对称aza-MBH反应

Scheme 20. Chiral thiourea-catalyzed asymmetric aza-MBH reaction of 2-aryl-3H-indol-3-ones with α,β-unsaturated γ-butyrolactams

图式21. 具有轴手性和中心手性的2,2-二取代吲哚啉-3-酮的合成

Scheme 21. Asymmetric synthesis of 2,2-disubstituted indolin-3-ones with axial and central chirality

图式22. 三组分催化2-芳基-3H-吲哚-3-酮与含γ-H的α,β-不饱和羧酸的不对称[4＋2]环化反应

Scheme 22. Asymmetric [4＋2] annulation of 2-aryl-3H-indole-3-ones with α,β-unsaturated carboxylic acids catalyzed by a three-component catalyst

图式23. (R)-CYC-9-CPA催化构筑2,3-二氢-1H-咪唑-[1,5-a]吲哚啉-9(9aH)-酮化合物

Scheme 23. Enantioselective construction of 2,3-dihydro-1H-imidazo [1,5-a]indolin-9(9aH)-ones catalyzed by (R)-CYC-9-CPA

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