Pd-catalyzed [3+2] Cycloaddition/Dearomatization of Indole-3-carboxylates with Trimethylenemethane

doi:10.6023/cjoc202602022

Chinese Journal of Organic Chemistry

ARTICLE

钯催化吲哚-3-羧酸酯和三亚甲基甲烷的环加成去芳构化反应

张青霞, 谢佳豪, 顾庆^*, 游书力^*

中国科学院上海有机化学研究所金属有机化学全国重点实验室新基石实验室上海 200032

收稿日期:2026-02-27 修回日期:2026-03-21
基金资助:
国家自然科学基金(No. 22393890、上海市科学技术委员会(23JC1404500)和上海市基础研究先行区计划资助项目.

Pd-catalyzed [3+2] Cycloaddition/Dearomatization of Indole-3-carboxylates with Trimethylenemethane

Qing-Xia Zhang, Jia-Hao Xie, Qing Gu^*, Shu-Li You^*

New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Received:2026-02-27 Revised:2026-03-21
Contact: ^*E-mail: slyou@sioc.ac.cn, qinggu@sioc.ac.cn
Supported by:
NSFC (22393890), Science and Technology Commission of Shanghai Municipality (23JC1404500) and Shanghai Pilot Program for Basic Research. S.-L.Y. acknowledges the support from New Cornerstone Science Foundation.

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Abstract

A formal [3+2] cycloaddition between indole-3-carboxylate derivatives and trimethylenemethane (TMM) donor is disclosed. The reaction proceeds smoothly in toluene at ambient conditions via a Pd-catalyzed dearomatization process, delivering a series of substituted 2,3-fused cyclopentannulated indolines (up to 99% yield). The reaction exhibits high functional group tolerance for indole derivatives under the standard conditions. Remarkably, the synthetic utility of this method was demonstrated by transformation of the products such as hydrolysis of ester, removal of Ts group, Sonogashira coupling reaction and reduction of ester and halogen.

Key words: cycloaddition, dearomatization, indole, palladium catalysis, trimethylenemethane

Cite this article

Qing-Xia Zhang, Jia-Hao Xie, Qing Gu, Shu-Li You. Pd-catalyzed [3+2] Cycloaddition/Dearomatization of Indole-3-carboxylates with Trimethylenemethane[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202602022.

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钯催化吲哚-3-羧酸酯和三亚甲基甲烷的环加成去芳构化反应

Pd-catalyzed [3+2] Cycloaddition/Dearomatization of Indole-3-carboxylates with Trimethylenemethane

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