C-3位五元螺环吲哚酮衍生物合成方法研究进展

doi:10.6023/cjoc202104008

摘要/Abstract

作为多种药物和天然产物的核心骨架结构, C-3位五元螺环吲哚酮衍生物在生物医药领域具有广泛的应用前景, 实现该类化合物的高效不对称合成一直是有机化学家的研究热点. 综述了近年来利用催化分子内反应、分子间反应和三组分反应不对称合成C-3位五元螺环吲哚酮衍生物的研究进展, 并对该领域的未来发展方向进行了展望.

关键词: 螺环吲哚酮, 合成方法, 不对称合成

As the core skeleton structure of many drugs and natural products, spirooxindole derivatives have a wide range of applications in the field of biology and medicine. Efficient synthesis of spirooxindole derivatives with high enantioselectivity and diastereoselectivity has gained much attention in organic chemical community. In this paper, the asymmetric synthetic methods for C-3 five-membered spirooxindoles by catalytic intramolecular reactions, intermolecular reactions and three- component reactions are reviewed. The future development direction of this field is also prospected.

Key words: spirooxindoles, synthetic method, asymmetric synthesis

引用此文

刘奕彤, 张茜苑, 苗志伟. C-3位五元螺环吲哚酮衍生物合成方法研究进展[J]. 有机化学, 2021, 41(10): 3965-3982.

Yitong Liu, Xiyuan Zhang, Zhiwei Miao. Research Progress on the Synthetic Method of Five-Membered Spirooxindole Derivatives at C-3 Position[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 3965-3982.

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图/表 38

图1. 带有五元螺环吲哚酮骨架结构的生物活性分子

Figure 1. Bioactive molecule with a core structure of five- member-ring fused spirooxindoles

图式1. 分子内亲核反应合成螺环吲哚酮

Scheme 1. Synthesis of spirooxindole via intramolecular nucleophilic reaction

图式2. 分子内Friedel-Crafts反应合成螺环吲哚酮

Scheme 2. Synthesis of spirooxindole via intramolecular Friedel-Crafts reaction

图式3. 分子内电环化反应合成螺环吲哚酮

Scheme 3. Synthesis of spirooxindole via intramolecular electrocyclization reaction

图式4. 氧化四氢-β-咔啉合成螺环吲哚酮

Scheme 4. Synthesis of spirooxindole by oxidation of tetrahydro-β-carboline

图式5. 氧化合成螺环吲哚酮的反应机理

Scheme 5. Mechanism for oxidation synthesis of spirooxindole

图式6. 碘化钠/过氧化氢催化的吲哚衍生物氧化/内酯化反应

Scheme 6. Oxidation/internal esterification of indole derivative catalyzed by NaI/H2O2

图式7. 胶束氧化剂催化合成螺环吲哚酮

Scheme 7. Synthesis of spirooxindole catalyzed by micellar oxidant

图式8. 钯催化呋喃衍生物不对称合成螺环吲哚酮

Scheme 8. Asymmetric synthesis of spirooxindole from furan derivatives catalyzed by palladium catalyst

图式9. 钯催化合成螺环吲哚酮反应机理

Scheme 9. Mechanism for synthesis of spirooxindole catalyzed by palladium catalyst

图式10. 选择性合成Z/E构型的螺环吲哚酮

Scheme 10. Selective synthesis of Z/E configuration spirooxindole

图式11. Z/E构型的螺环吲哚酮合成机理

Scheme 11. Mechanism for synthesis of Z/E configuration spirooxindole

图式12. 铱催化剂催化N-(2-碘苯基)酰胺合成螺环吲哚酮

Scheme 12. Synthesis of spirooxindole by N-(2-iodophenyl) amide catalyzed by iridium

图式13. 铱催化剂催化合成螺环吲哚酮机理

Scheme 13. Mechanism for synthesis of spirooxindole over iridium catalyst

图式14. 钯催化N-(2-三氟甲磺酸酯基苯基)酰胺合成螺环吲哚酮

Scheme 14. Synthesis of spirooxindole by N-(2-trifluoromethesulfonatephenyl) amide catalyzed by Pd

图式15. 累积双烯和吲哚酮亚胺反应合成五元、六元螺环吲哚酮

Scheme 15. Synthesis of spirooxindole with a five- or six-member-ring produced by allene and ketone imide

图式16. 累积双烯与酮亚胺反应合成五元螺环吲哚酮反应机理

Scheme 16. Mechanism for synthesis of five-member-ring spirooxindole from allene and ketone imide

图式17. 累积双烯与吲哚酮衍生物合成螺环吲哚酮

Scheme 17. Reaction between allene and oxindole derivative to construct spirooxindole

图式18. 累积双烯与吲哚酮衍生物反应机理

Scheme 18. Mechanism for reaction between allene and oxindole derivatives

图式19. 吲哚酮衍生物和MBH膦酸酯的[3+2]环化反应

Scheme 19. [3+2] annulation between oxindole derivative and MBH phosphate ester

图式20. 吲哚酮衍生物和MBH膦酸酯合成螺环吲哚酮反应机理

Scheme 20. Mechanism for reaction between oxindole derivative and MBH phosphate ester to construct spirooxindole

图式21. 吲哚酮衍生物和炔合成螺环吲哚酮

Scheme 21. Synthesis of spirooxindole by oxindole derivative and alkyne

图式22. 膦试剂催化合成五元螺环吲哚酮反应机理

Scheme 22. Mechanism for synthesis of spirooxindole catalyzed by phosphine

图式23. 手性胺试剂催化合成螺环吲哚酮

Scheme 23. Synthesis of spirooxindole catalyzed by chiral amine

图式24. 双功能吲哚酮和α,β-不饱和醛的[3+2]环化反应

Scheme 24. [3+2] annulation between bifundational oxindole and α,β-unsaturated aldehyde

图式25. 镍催化[4+1]环化反应合成螺环吲哚酮

Scheme 25. [4+1] annulation to construct spirooxindole catalyzed by Nickel

图式26. 镍催化合成五元螺环吲哚酮反应机理

Scheme 26. Mechanism for synthesis of five-member-ring spirooxindole catalyzed by Ni

图式27. 金属镍催化[3+2]环化反应合成五元螺环吲哚酮

Scheme 27. [3+2] annulation to construct five-member-ring spirooxindole catalyzed by Ni

图式28. 利用靛红衍生物、2-氨基丙二酸二乙酯和丁炔二酸二酯合成螺环吲哚酮

Scheme 28. Reaction between isatin, propanedioic acid and dimethyl acetylenedicarboxylate to construct spirooxindole

图式29. 三组分环加成反应合成螺环吲哚酮反应机理

Scheme 29. Mechanism for three components cycloaddition to synthetize spirooxindole

图式30. 合成带有孕烯醇酮结构的五元螺环吲哚酮

Scheme 30. Synthesis of five-member-ring spirooxindole with pregnenolone

图式31. 手性磷酸催化的三组分1,3-偶极环加成反应

Scheme 31. Three component 1,3-dipolar cycloaddition catalyzed by chiral phosphoric acid

图式32. 吲哚酮和邻苯二甲醛合成螺环吲哚酮

Scheme 32. Reaction between oxindole and o-phthalaldehyde to construct spirooxindole

图式33. 吲哚酮和邻苯二甲醛反应机理

Scheme 33. Mechanism for reaction between oxindole and o-phthalaldehyde

图式34. 手性胺催化多组分反应合成螺环吲哚酮

Scheme 34. Multi-component reaction to synthetize spirooxindole catalyzed by chiral amine

图式35. 手性铜配体催化[3+2]环加成反应

Scheme 35. [3+2] Cycloaddition catalyzed by chiral Cu complex

图式36. 靛红衍生物、丙二腈和α-羟基酮反应合成螺环吲哚酮结构

Scheme 36. Reaction between isatin derivatives, malononitrile and α-hydroxylketones to synthesize spirooxindoles

图式37. 靛红衍生物、丙二腈和α-羟基酮反应机理

Scheme 37. Mechanism for reaction between isatin derivatives, malononitrile and α-hydroxylketones to synthesize spirooxindoles

参考文献 38

[1]	Mei, G.-J.; Shi, F. Chem. Commun. 2018, 54, 6607. doi: 10.1039/C8CC02364F
[2]	Cui, C.-B.; Kakeya, H.; Osada, H. Tetrahedron 1996, 52, 12651. doi: 10.1016/0040-4020(96)00737-5
[3]	Cui, C.-B.; Kakeya, H.; Osada, H. J. Antibiot. 1996, 49, 832. pmid: 8823522
[4]	Watson, A. F.; Liu, J.-F.; Bennaceur, K.; Drummond, C. J.; Endicott, J. A.; Golding, B. T.; Griffin, R. J.; Haggerty, K.; Lu, X.-H.; McDonnell, J. M.; Newell, D. R.; Noble, M. E. M.; Revill, C. H.; Riedinger, C.; Xu, Q.; Zhao, Y.; Lunec, J.; Hardcastle, L. R. Bioorg. Med. Chem. Lett. 2011, 21, 5916. doi: 10.1016/j.bmcl.2011.07.084 pmid: 21875801
[5]	Zhou, J.-Y.; Zhou, S.-W. J. Ethnopharmacol. 2010, 132, 15. doi: 10.1016/j.jep.2010.08.041
[6]	Xiao, Y.-L.; Zhou, Y.; Wang, J.; Wang, J.-X.; Liu, H. Chin. J. Org. Chem. 2015, 35, 2035. (in Chinese) doi: 10.6023/cjoc201504045
	(肖永龙, 周宇, 王江, 王进欣, 柳红, 有机化学, 2015, 35, 2035.) doi: 10.6023/cjoc201504045
[7]	Ohmatsu, K.; Ando, Y.; Nakashima, T.; Ooi, T. Chem 2016, 1, 802. doi: 10.1016/j.chempr.2016.10.012
[8]	Yin, B.-L.; Lai, J.-Q.; Zhang, Z.-R.; Jiang, H.-F. Adv. Synth. Catal. 2011, 353, 1961. doi: 10.1002/adsc.v353.11/12
[9]	Yin, B.-L.; Huang, L.; Zhang, X.-Y.; Ji, F.-H.; Jiang, H.-F. J. Org. Chem. 2012, 77, 6365. doi: 10.1021/jo301039y
[10]	Yin, B.-L.; Huang, L.; Wang, X.-J.; Liu, J.-C.; Jiang, H.-F. Adv. Synth. Catal. 2013, 355, 370.
[11]	Yin, X.-P.; Zeng, X.-P.; Liu, Y.-L.; Liao, F.-M.; Yu, J.-S.; Zhou, F.; Zhou, J. Angew. Chem., Int. Ed. 2014, 53, 13740. doi: 10.1002/anie.201407677
[12]	Nakagawa, M.; Matsuki, K.; Hasegawa, K.; Hino, T. J. Chem. Soc., Chem. Commun. 1982, 742.
[13]	Xu, J.; Liang, L.-X.; Zheng, H.-H.; Chi, Y.-R.; Tong, R.-B. Nat. Commun. 2019, 10, 4754. doi: 10.1038/s41467-019-12768-4
[14]	Li, G.-F.; Huang, L.-W.; Xu, J.-C.; Sun, W.-S.; Xie, J.-Q.; Hong, L.; Wang, R. Adv. Synth. Catal. 2016, 358, 2873. doi: 10.1002/adsc.201600441
[15]	Wang, D.-G.; Lu, X.-B.; Sun, S.-H.; Yu, H.-B.; Su, H.-M.; Wu, Y.-Z.; Zhong, F.-R. Eur. J. Org. Chem. 2019, 6028.
[16]	Liu, J.-C.; Peng, H.; Lu, L.; Xu, X.-B.; Jiang, H.-F.; Yin, B.-L. Org. Lett. 2016, 18, 6440. doi: 10.1021/acs.orglett.6b03339
[17]	Liu, J.-C.; Xu, X.-B.; Li, J.-Y.; Liu, B.; Jiang, H.-F.; Yin, B.-L. Chem. Commun. 2016, 52, 9550. doi: 10.1039/C6CC04298H
[18]	Liu, J.-C.; Peng, H.; Yang, Y.-J.; Jiang, H.-F.; Yin, B.-L. J. Org. Chem. 2016, 81, 9695. doi: 10.1021/acs.joc.6b01774
[19]	Chen, J.-Q.; Wei, Y.-L.; Xu, G.-Q.; Liang, Y.-M.; Xu, P.-F. Chem. Commun. 2016, 52, 6455. doi: 10.1039/C6CC02007K
[20]	Ratushnyy, M.; Kvasovs, N.; Sarkar, S.; Gevorgyan, V. Angew. Chem., Int. Ed. 2020, 59, 10316. doi: 10.1002/anie.v59.26
[21]	Ying, A.-G.; Wu, C.-L.; Fu, Y.-Q.; Ren, S.-B.; Liang, H.-D. Chin. J. Org. Chem. 2012, 32, 1587. (in Chinese) doi: 10.6023/cjoc201203009
	(应安国, 武承林, 付永前, 任世斌, 梁华定, 有机化学, 2012, 32, 1587.) doi: 10.6023/cjoc201203009
[22]	Sankar, M. G.; Castro, M. G.; Golz, C.; Strohmann, C.; Kumar, K.; Ihsar, M. P. S. Angew. Chem., Int. Ed. 2016, 55, 9709. doi: 10.1002/anie.201603936
[23]	Feng, J.-X.; Huang, Y. Chem. Commun. 2019, 55, 14011. doi: 10.1039/C9CC07346A
[24]	Yu, C.-B.; Zheng, W.-P.; Zhan, J.-C.; Sun, Y.-C.; Miao, Z.-W. RSC Adv. 2014, 4, 63246. doi: 10.1039/C4RA12997K
[25]	Zhang, J.-Y.; Cheng, C.; Wang, D.; Miao, Z.-W. J. Org. Chem. 2017, 82, 10121. doi: 10.1021/acs.joc.7b01582
[26]	Lin, Y.; Du, D.-M. Chin. J. Org. Chem. 2020, 40, 3214. (in Chinese) doi: 10.6023/cjoc202005065
	(林晔, 杜大明, 有机化学, 2020, 40, 3214.) doi: 10.6023/cjoc202005065
[27]	Duan, S.-W.; Li, Y.; Liu, Y.-Y.; Zou, Y.-Q.; Shi, D.-Q.; Xiao, W.-J. Chem. Commun. 2012, 48, 5160. doi: 10.1039/c2cc30931a
[28]	Ding, L.-Z.; Zhong, T.-S.; Wu, H.; Wang, Y.-M. Eur. J. Org. Chem. 2014, 5139.
[29]	Buxton, C. S.; Blakemore, D. C.; Bower, J. F. Angew. Chem., Int. Ed. 2017, 56, 13824. doi: 10.1002/anie.201707531
[30]	Zhou, P.-F.; Cai, Y.-F.; Lin, L.-L.; Lian, X.-J.; Xia, Y.; Liu, X.-H.; Feng, X.-M. Adv. Synth. Catal. 2015, 357, 695. doi: 10.1002/adsc.v357.4
[31]	Tan, W.; Zhu, X.-T.; Zhang, S.; Xing, G.-J.; Zhu, R.-Y.; Shi, F. RSC Adv. 2013, 3, 10875. doi: 10.1039/c3ra40874d
[32]	Yu, B.; Sun, X.-N. Shi, X.-J.; Qi, P.-P.; Zheng, Y.-C.; Yu, D.-Q.; Liu, H.-M. Steroids 2015, 102, 92. doi: 10.1016/j.steroids.2015.08.003
[33]	Shi, F.; Tao, Z.-L.; Luo, S.-W.; Tu, S.-J.; Gong, L.-Z. Chem.-Eur. J. 2012, 18, 6885. doi: 10.1002/chem.201200358
[34]	Guo, C.; Song, J.; Gong, L.-Z. Org. Lett. 2013, 15, 2676. doi: 10.1021/ol400983j
[35]	Yang, J.; Liu, X.-W.; Wang, D.-D.; Tian, M.-Y.; Han, S.-N.; Feng, T.-T.; Liu, X.-L.; Mei, R.-Q.; Zhou, Y. Tetrahedron 2016, 72, 8523. doi: 10.1016/j.tet.2016.10.050
[36]	Wu, M.-Y.; He, W.-W.; Liu, X.-Y.; Tan, B. Angew. Chem., Int. Ed. 2015, 54, 9409. doi: 10.1002/anie.201504640
[37]	Salahi, F.; Taghizadeh, M. J.; Arvinnezhad, H.; Moemeni, M.; Jadidi, K.; Notas, B. Tetrahedron Lett. 2014, 55, 1515. doi: 10.1016/j.tetlet.2013.11.097
[38]	Miao, Y.-H.; Hua, Y.-Z.; Wang, M.-C. Org. Biomol. Chem. 2019, 17, 7172. doi: 10.1039/C9OB01233H