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0 202605026

DOI: https://doi.org/10.6023/cjoc202605026

ARTICLE

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

  • Qianwei Zhang ,
  • Ling-Quan Kong ,
  • Zili Chen ,
  • Zhi-Xiang Yu
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  • aBeijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871;
    bDepartment of Chemistry, Renmin University of China, Beijing, 100872

Received date: 2026-05-25

  Revised date: 2026-07-27

  Online published: 2026-08-17

Supported by

NSFC-ISF (No. 22361142835) and high-performance computing platform of Peking University

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Abstract

A formal [6+2-1] reaction between benzoquinones and alkynes mediated by BF3, giving tropones and liberating carbon monoxide, was discovered by Chen previously. Report here is the mechanistic investigation of this [6+2-1] reaction through DFT calculations, finding 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-alkyl2-aryl alkynes as the 2-π components were used.

Key words： [6+2-1] Cycloaddition; Mechanistic study; Benzoquinones

Cite this article

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, 0 : 202605026 . DOI: 10.6023/cjoc202605026

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