Cascade Cyclization Reaction Initiated by Benzylic Carbocation of Indole: Scope and Mechanistic Insights

doi:10.6023/cjoc202102006

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (8): 3126-3133.DOI: 10.6023/cjoc202102006 Previous Articles Next Articles

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吲哚苄位碳正离子引发的串联环化反应的普适性和机理探究

高中润, 王媛, 宋航, 徐正仁^*(), 贾彦兴^*()

北京大学药学院天然药物及仿生药物国家重点实验室北京 100191

收稿日期:2021-02-01 修回日期:2021-05-02 发布日期:2021-05-25
通讯作者: 徐正仁, 贾彦兴
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21871013)

Cascade Cyclization Reaction Initiated by Benzylic Carbocation of Indole: Scope and Mechanistic Insights

Zhongrun Gao, Yuan Wang, Hang Song, Zhengren Xu(), Yanxing Jia()

State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences,Peking University, Beijing 100191

Received:2021-02-01 Revised:2021-05-02 Published:2021-05-25
Contact: Zhengren Xu, Yanxing Jia
About author:
† (These authors contributed equally to this work).
Supported by:
National Natural Science Foundation of China(21871013)

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Abstract

During the course of the total synthesis of α-cyclopianic acid (α-CPA) and speradine C, our research group have developed a biomimetic cascade cyclization reaction initiated by the benzylic carbocation of indole. In this paper, the scope and the reaction mechanism of the cascade cyclization reaction were studied. The experimental results show that the cascade cyclization reaction occurrs at the benzylic carbocation of indole, indicating that the conjugation effect of the indole nitrogen atom plays a key role in the cascade cyclization of benzylic carbocations.

Key words: mechanism, cascade cyclization, benzylic carbocation, indole, conjugation effect

Cite this article

Zhongrun Gao, Yuan Wang, Hang Song, Zhengren Xu, Yanxing Jia. Cascade Cyclization Reaction Initiated by Benzylic Carbocation of Indole: Scope and Mechanistic Insights[J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3126-3133.

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Fig. & Tab. 8

Scheme 1. Biosynthesis of α-CPA

Scheme 2. A possible mechanism for [3+2] annulation

Scheme 3. Attempt on cyclization of compound 10

Scheme 4. Attempt on cyclization of compound 14

Scheme 5. Attempt on cyclization of compound 18

Scheme 6. Attempt on cyclization of compound 22

Scheme 7. Attempt on cyclization of compound 26

Scheme 8. A possible mechanism for [4+2] annulation

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吲哚苄位碳正离子引发的串联环化反应的普适性和机理探究

Cascade Cyclization Reaction Initiated by Benzylic Carbocation of Indole: Scope and Mechanistic Insights

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