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Chinese Journal of Organic Chemistry >

2025 , Vol. 45 >Issue 3: 1021 - 1029

DOI: https://doi.org/10.6023/cjoc202406048

ARTICLES

Enantiodivergent Synthesis of (+)- and (–)-Crispine A

  • Yanben Wang ,
  • Zuming Lin ,
  • Sha-Hua Huang ,
  • Lili Zhu ,
  • Ran Hong
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  • a School of Environmental and Chemical Engineering, Shanghai Institute of Technology, Shanghai 201418
    b State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
†(These authors contributed equally to this work).
* E-mail: ;
* E-mail: ;

Received date: 2024-06-29

  Revised date: 2024-08-22

  Online published: 2024-09-27

Supported by

National Natural Science Foundation of China(22271194); National Natural Science Foundation of China(22371295); National Natural Science Foundation of China(U24A20484); Science and Technology Commission of Shanghai Municipality(20XD1404700)

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Abstract

Crispine A is a representative alkaloid bearing pyrrolo[2,1-a]isoquinoline to exhibit various biological activities. In this report, enantiodivergent synthesis of crispine A has been achieved, featuring a stereoselective 1,3-dipolar cycloaddition and an enzymatic kinetic resolution. The sequential process including cleavage of the N—O bond and cyclization proved to be effective and practical toward pyrrolo[2,1-a]isoquinoline in intriguing bioactive alkaloids. The capacity of enzymatic resolution dictated in this work is of great interest to accumulate the tetrahydroisoquinoline (THIQ)-fused pyrrolidine which is commonly embedded in various bioactive compounds.

Key words： chemoenzymatic synthesis; dipolar cycloaddition; enantiodivergent synthesis; kinetic resolution; nitrone

Cite this article

Yanben Wang , Zuming Lin , Sha-Hua Huang , Lili Zhu , Ran Hong . Enantiodivergent Synthesis of (+)- and (–)-Crispine A[J]. Chinese Journal of Organic Chemistry, 2025 , 45(3) : 1021 -1029 . DOI: 10.6023/cjoc202406048

References

[1]
Chrzanowska, M.; Grajewska, A.; Rozwadowska, M. D. Chem. Rev. 2016, 116, 12369 and earlier reviews cited therein.
[2]
Kim, A. N.; Ngamnithiporn, A.; Du, E.; Stoltz, B. M. Chem. Rev. 2023, 123, 9447.
[3]
Tao, S.; Wang, Y.; Hong, R.; Huang, S.-H. Molecules 2022, 27, e4324.
[4]
Matveeva, M. D.; Purgatorio, R.; Voskressensky, L. G.; Altomare, C. D. Future Med. Chem. 2019, 11, 2735.
[5]
Fahmy, N. M.; Al-Sayed, E.; El-Shazly, M.; Singab, A. N. Nat. Prod. Res. 2020, 34, 1891.
[6]
Fukuda, T.; Ishibashi, F.; Iwao, M. Lamellarin alkaloids: Isolation, synthesis, and biological activity. In The Alkaloids: Chemistry and Biology, Ed.: Knölker, H.-J., Academic Press, London 83, pp. 1-112.
[7]
Cui, H.-L. Org. Biomol. Chem. 2022, 20, 2779.
[8]
Zhang, Q.; Tu, G.; Zhao, Y.; Cheng, T. Tetrahedron 2002, 58, 6795.
[9]
Child, R.; Pyman, F. L. J. Chem. Soc. 1931, 36.
[10]
Mohan, C.; R. Krishna, B.; Sivanandan, S. T.; Ibnusaud, I. Eur. J. Org. Chem. 2021, 4911.
[11]
Yang, L.; Li, J.; Xu, Z.; Yao, P.; Wu, Q.; Zhu, D.; Ma, Y. Org. Lett. 2022, 24, 6531.
[12]
Szawkało, J.; Zawadzka, A.; Wojtasiewicz, K.; Leniewski, A.; Drabowiczb, J.; Czarnocki, Z. Tetrahedron: Asymmetry 2005, 16, 3619.
[13]
Yu, H.-H.; Yu, Z.-P.; Capon, R. J.; Zhang, H. Molecules 2022, 27, e1279.
[14]
Huang, S.-H.; Li, W.; Chen, L.; Xu, J.; Hong, R. Bioresour. Bioprocess. 2015, 2, e10.
[15]
Li, W.; Lin, Z.; Chen, L.; Tian, X.; Wang, Y.; Huang, S.-H.; Hong, R. Tetrahedron Lett. 2016, 57, 603.
[16]
Yang, L.; Lin, Z.; Shao, S.; Zhao, Q.; Hong, R. Angew. Chem. Int. Ed. 2018, 57, 16200.
[17]
Yang, L.; Lin, Z.; Zheng, K.; Kong, L.; Hong, R. Chin. J. Chem. 2020, 38, 725.
[18]
Peng, Y.; Lin, Z.; Zhu, L.; Han, S.; Huang, S.-H.; Hong, R. Chin. J. Chem. 2024, 42, 841.
[19]
Murahashi, S.-I.; Imada, Y. Chem. Rev. 2019, 119, 4684.
[20]
Tufariello, J. J. Acc. Chem. Res. 1979, 12, 396.
[21]
Confalone, P. N.; Huie, E. M. The [3+2] nitrone-olefin cycloaddition reaction In Organic Reactions, Vol. 36, Ed.: Kende, A. S., John Wiley & Sons, 1988, pp. 1-173.
[22]
Zhao, B. X.; Yu, Y.; Eguchi, S. Org. Prep. Proc. Int. 1997, 29, 185.
[23]
Brandi, A.; Cardona, F.; Cicchi, S.; Cordero, F. M.; Goti, A. [3+2] dipolar cycloadditions of cyclic nitrones with alkenes In Organic Reactions, Vol. 94, Ed.: Denmark, S. E., John Wiley & Sons, 2017, pp. 1-529.
[24]
Gotor-Fermández, V.; Busto, E.; Gotor, V. Adv. Synth. Catal. 2006, 348, 797.
[25]
Greenhalgh, M. D.; Taylor, J. E.; Smith, A. D. Tetrahedron 2018, 74, 5554.
[26]
Schmid, H.; Karrer, P. Helv. Chim. Acta 1949, 32, 1371.
[27]
Forró, E.; Schönstein, L.; Fülöp, F. Tetrahedron: Asymmetry 2011, 22, 1255.
[28]
Orsy, G.; Forró, E. Molecules 2023, 28, e6362.
[29]
Wang, J.; Gong, F.; Liang, T.; Xie, Z.; Yang, Y.; Cao, C.; Gao, J.; Lu, T.; Chen, X. Eur. J. Med. Chem. 2021, 225, 113815.
[30]
Tian, X.; Xuan, T.; Gao, J.; Zhang, X.; Liu, T.; Luo, F.; Pang, R.; Shao, P.; Yang, Y.-F.; Wang, Y. Nat. Commun. 2024, 15, 6429.
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