苯并醌与炔烃的形式[6＋2−1]环加成反应的机理研究

doi:10.6023/cjoc202605026

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3624-3629.DOI: 10.6023/cjoc202605026 上一篇下一篇

研究论文

苯并醌与炔烃的形式[6＋2−1]环加成反应的机理研究

张谦玮^a, 孔令荃^a, 陈自立^b, 余志祥^a^,^*()

^a 北京大学化学与分子工程学院生物有机与分子工程教育部重点实验室北京 100871
^b 中国人民大学化学系北京 100872

收稿日期:2026-05-25 修回日期:2026-07-27 发布日期:2026-08-03
基金资助:
国家自然科学基金(22361142835); 北京大学高性能计算校级公共平台资助项目.

Mechanistic Study of the Formal [6＋2−1] Cycloaddition of Benzoquinones and Alkynes to Tropones

Qianwei Zhang^a, Ling-Quan Kong^a, Zili Chen^b, Zhi-Xiang Yu^a^,^*()

^a Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871
^b Department of Chemistry, Renmin University of China, Beijing, 100872

Received:2026-05-25 Revised:2026-07-27 Published:2026-08-03
Contact:
^* E-mail: yuzx@pku.edu.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Natural Science Foundation of China(22361142835); High-Performance Computing Platform of Peking University.

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摘要/Abstract

在三氟化硼促进下, 苯并醌与炔烃之间可发生形式上的[6＋2−1]反应生成环庚三烯酮产物, 并释放一分子一氧化碳. 我们的密度泛函理论(DFT)计算发现, [6＋2−1]反应经由炔与底物中的醌的Diels-Alder (D-A)反应引发再发生骨架重排的机理非常困难, 原因是这一过程中D-A反应涉及去芳构化过程, 需要非常高的活化能. 为此, 提出一种新的机理, 认为反应始于炔烃对苯并醌中羰基(与BF₃配位)的亲核进攻, 再经过Friedel-Crafts型加成反应得到桥环[3.2.1]中间体, 最后通过脱除一氧化碳分子来产生环庚三烯酮产物. 这一机理得到DFT计算的支持, 并可以解释为什么在使用1-烷基-2-芳基乙炔作为底物时反应能够实现较高的区域选择性.

关键词: [6＋2−1]环加成, 机理研究, 苯并醌, 环庚三烯酮

A formal [6＋2−1] reaction between benzoquinones and alkynes mediated by BF₃, giving tropones and liberating carbon monoxide, was discovered by Chen previously. A mechanistic investigation of this [6＋2−1] reaction through density functional theory (DFT) calculations was reported. Our study reveals that the originally proposed mechanism involving energetically demanding dearomative Diels-Alder (D-A) reaction between benzoquinones and alkynes, followed by a skeleton rearrangement, is difficult. Instead, the [6＋2−1] reaction starts from a nucleophilic attack of alkynes to the carbonyl of benzoquinones coordinated to BF₃, followed by Friedel-Crafts type addition, giving intermediates with a [3.2.1] skeleton, which then release carbon monoxide and the final tropones. The substituent effects on the regioselectivity of this [6＋2−1] reaction have also been studied when 1-alkyl-2-aryl acetylenes as the 2-π components were used.

Key words: [6＋2−1] cycloaddition, mechanistic study, benzoquinones, tropones

引用此文

张谦玮, 孔令荃, 陈自立, 余志祥. 苯并醌与炔烃的形式[6＋2−1]环加成反应的机理研究[J]. 有机化学, 2026, 46(9): 3624-3629.

Qianwei Zhang, Ling-Quan Kong, Zili Chen, Zhi-Xiang Yu. Mechanistic Study of the Formal [6＋2−1] Cycloaddition of Benzoquinones and Alkynes to Tropones[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3624-3629.

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图/表 6

Scheme 1. Selected cycloaddition reactions for the synthesis of tropones

Scheme 2. Originally and newly proposed mechanisms of [6＋2−1] reaction of benzoquinones and alkynes mediated by BF3

Figure 1. (a) Gibbs free energy profile of the non-catalyzed D-A reaction pathway; (b) Gibbs free energy profile of the BF3-catalyzed D-A reaction pathway

Figure 2. (a) Gibbs free energy profile of new pathway; (b) Structures of key intermediate and transition states

Figure 3. Explanation for the regioselectivity reported by Chen group (Gibbs free energies are given in reference to the sum of dibenzoquinone 1e, alkyne 2e and BF3•Et2O)

Figure 4. Calculations of other possible pathways for the [6＋2－1] reaction

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苯并醌与炔烃的形式[6＋2−1]环加成反应的机理研究

Mechanistic Study of the Formal [6＋2−1] Cycloaddition of Benzoquinones and Alkynes to Tropones

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