Total Synthesis of Dimeric HPI Alkaloids

doi:10.1007/s13659-016-0092-8

Natural Products and Bioprospecting ›› 2016, Vol. 6 ›› Issue (2): 117-139.DOI: 10.1007/s13659-016-0092-8

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Total Synthesis of Dimeric HPI Alkaloids

Xianfu Shen, Yongyun Zhou, Yongkai Xi, Jingfeng Zhao, Hongbin Zhang

Key Laboratory of Medicinal Chemistry for Natural Resource(Yunnan University), Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming 650091, People's Republic of China

Received:2016-01-13 Revised:2016-02-19 Online:2018-02-08 Published:2016-04-24
Supported by:
This work was supported by Grants from Natural Science Foundation of China (20925205 and 21332007);the Program for Changjiang Scholars and Innovative Research Team in University (IRT13095);Yunnan Provincial Science and Technology Department (2010GA014) and the Program for Yunling Scholars.Dr.Xiaonian Li of the Kunming Institute of Botany is gratefully acknowledged for X-ray crystallographic analysis of compound 23.CCDC 1409209(23)

Total Synthesis of Dimeric HPI Alkaloids

Xianfu Shen, Yongyun Zhou, Yongkai Xi, Jingfeng Zhao, Hongbin Zhang

Key Laboratory of Medicinal Chemistry for Natural Resource(Yunnan University), Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming 650091, People's Republic of China

通讯作者: Hongbin Zhang,e-mail:zhanghb@ynu.edu.cn
基金资助:
This work was supported by Grants from Natural Science Foundation of China (20925205 and 21332007);the Program for Changjiang Scholars and Innovative Research Team in University (IRT13095);Yunnan Provincial Science and Technology Department (2010GA014) and the Program for Yunling Scholars.Dr.Xiaonian Li of the Kunming Institute of Botany is gratefully acknowledged for X-ray crystallographic analysis of compound 23.CCDC 1409209(23)

Abstract

Abstract: In this paper, we report a full account of the synthesis of dimeric hexahydropyrroloindole alkaloids and its analogues. The key feature of our new strategy is the novel catalytic copper (10%) mediated intramolecular arylations of o-haloanilides followed by intermolecular oxidative dimerization of the resulting oxindoles in one pot. This sequential reaction leads to the key intermediates for the synthesis of (+)-chimonanthine, (+)-folicanthine, (-)-calycanthine and (-)-ditryptophenaline. Graphical Abstract In the presence of catalytic amount of cuprous iodide (10%), an intramolecular arylation of ohaloanilidesfollowedby an intermolecularoxidative dimerizationof the resultingoxindolesleads to a commonintermediatefor the synthesis of (+)-chimonanthine, (+)-folicanthine and (-)-calycanthine. Based on this cascade sequence, we also developed a flexible strategy towards the asymmetric syntheses of dimeric HPI alkaloids (-)-ditryptophenaline and its analogues.

Key words: Copper catalyzed reaction, Oxidative dimerization, Total synthesis, Hexahydropyrroloindole, Alkaloids

摘要： In this paper, we report a full account of the synthesis of dimeric hexahydropyrroloindole alkaloids and its analogues. The key feature of our new strategy is the novel catalytic copper (10%) mediated intramolecular arylations of o-haloanilides followed by intermolecular oxidative dimerization of the resulting oxindoles in one pot. This sequential reaction leads to the key intermediates for the synthesis of (+)-chimonanthine, (+)-folicanthine, (-)-calycanthine and (-)-ditryptophenaline. Graphical Abstract In the presence of catalytic amount of cuprous iodide (10%), an intramolecular arylation of ohaloanilidesfollowedby an intermolecularoxidative dimerizationof the resultingoxindolesleads to a commonintermediatefor the synthesis of (+)-chimonanthine, (+)-folicanthine and (-)-calycanthine. Based on this cascade sequence, we also developed a flexible strategy towards the asymmetric syntheses of dimeric HPI alkaloids (-)-ditryptophenaline and its analogues.

关键词: Total synthesis, Hexahydropyrroloindole, Alkaloids, Copper catalyzed reaction, Oxidative dimerization

Xianfu Shen, Yongyun Zhou, Yongkai Xi, Jingfeng Zhao, Hongbin Zhang. Total Synthesis of Dimeric HPI Alkaloids[J]. Natural Products and Bioprospecting, 2016, 6(2): 117-139.

Xianfu Shen, Yongyun Zhou, Yongkai Xi, Jingfeng Zhao, Hongbin Zhang. Total Synthesis of Dimeric HPI Alkaloids[J]. 应用天然产物, 2016, 6(2): 117-139.

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Total Synthesis of Dimeric HPI Alkaloids

Total Synthesis of Dimeric HPI Alkaloids

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