通过苄醇与炔烃的环化反应快速高效构建茚及螺环茚

doi:10.6023/cjoc201808009

有机化学 ›› 2019, Vol. 39 ›› Issue (1): 223-231.DOI: 10.6023/cjoc201808009 上一篇下一篇

所属专题：庆祝陈庆云院士九十华诞

研究论文

通过苄醇与炔烃的环化反应快速高效构建茚及螺环茚

余佳佳^a, 杨珊^a, 吴镇^a, 朱晨^a,b

a 苏州大学材料与化学化工学部苏州 215123;
b 中国科学院上海有机化学研究所天然产物有机合成重点实验室上海 200032

收稿日期:2018-08-10 修回日期:2018-09-10 发布日期:2018-10-12
通讯作者: 朱晨 E-mail:chzhu@suda.edu.cn
基金资助:
国家自然科学基金（No.21722205）资助项目.

Annulation of Benzylic Alcohols with Alkynes for Rapid and Efficient Synthesis of Indenes and Spiroindenes

Yu Jiajia^a, Yang Shan^a, Wu Zhen^a, Zhu Chen^a,b

a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123;
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Shanghai 200032

Received:2018-08-10 Revised:2018-09-10 Published:2018-10-12
Contact: 10.6023/cjoc201808009 E-mail:chzhu@suda.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21722205).

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1. 通过苄醇与炔烃的环化反应快速高效构建茚及螺环茚.PDF(1942KB)

摘要/Abstract

作为一类重要的碳环化合物，茚、螺环茚及其衍生物常见于各种天然产物骨架结构中，并作为合成中间体广泛地应用于材料、医药、有机不对称合成等领域.在路易斯酸TiCl₄或AlCl₃作用下，二苯甲醇或芳基取代环醇等苄醇通过生成碳正离子中间体，与炔烃进行环化反应高效合成多种茚及螺环茚.该反应仅需30 min，反应过程中完成了2个新C—C键的构建，对具有各种取代基的炔烃均有较好的适用性.芳基取代的环丁醇、环己醇、环庚醇、环辛醇以及环十二醇都可以适用于该方法，多样性地构建多种有合成价值的螺环骨架.该方法具有操作简便、反应时间短、条件温和等优点.

关键词: 路易斯酸, 环化反应, 茚, 螺环茚

As a type of important carbocyclic compounds, indenes and spiroindenes are not only widely found in natural products but extensively employed as synthetic building blocks in materials, pharmaceuticals, and asymmetric synthesis. An efficient and rapid synthesis of indenes and spiroindenes via the annulation of benzylic alcohols (or aryl-substituted cycloalkanols) with alkynes in the presence of TiCl₄ or AlCl₃ was desclosed. This reaction is normally completed within 30 min at room temperature and compatible with a variety of substituted alkynes. Two new C—C bonds are constructed during the reaction. Cycloalkanols such as cyclobutanol, cyclohexanol, cycloheptanol, cyclooctanol, and cyclododecanol are suitable substrates to afford a set of valuable spiroindenes. This method is featured with simple operation, short reaction time, and mild reaction conditions.

Key words: Lewis acid, cyclization, indene, spiroindene

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余佳佳, 杨珊, 吴镇, 朱晨. 通过苄醇与炔烃的环化反应快速高效构建茚及螺环茚[J]. 有机化学, 2019, 39(1): 223-231.

Yu Jiajia, Yang Shan, Wu Zhen, Zhu Chen. Annulation of Benzylic Alcohols with Alkynes for Rapid and Efficient Synthesis of Indenes and Spiroindenes[J]. Chin. J. Org. Chem., 2019, 39(1): 223-231.

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通过苄醇与炔烃的环化反应快速高效构建茚及螺环茚

Annulation of Benzylic Alcohols with Alkynes for Rapid and Efficient Synthesis of Indenes and Spiroindenes

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