Mathis Lefebvre, Paul A Johnson, Pierre Deslongchamps
{"title":"The Mechanism of the Cycloaddition of Substituted Ketenes to Cyclopentadiene Based on the Bent Bond/Antiperiplanar Hypothesis Orbital Model.","authors":"Mathis Lefebvre, Paul A Johnson, Pierre Deslongchamps","doi":"10.1021/acs.joc.4c02083","DOIUrl":null,"url":null,"abstract":"<p><p>The [2 + 2] cycloaddition of substituted ketenes with cyclopentadiene producing bicyclo[3.2.0]hept-2-en-6-ones is rationalized by the Bent Bond/Antiperiplanar Hypothesis (BBAH) orbital model. With monosubstituted ketenes, the <i>endo</i> isomer is formed preferentially. The <i>endo</i> and <i>exo</i> isomers are both produced with the cyclobutanone ring in the <b>co-folded in</b> conformation. Computational results support the analysis of the BBAH based mechanism in agreement with experimental results.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3000,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.joc.4c02083","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
The [2 + 2] cycloaddition of substituted ketenes with cyclopentadiene producing bicyclo[3.2.0]hept-2-en-6-ones is rationalized by the Bent Bond/Antiperiplanar Hypothesis (BBAH) orbital model. With monosubstituted ketenes, the endo isomer is formed preferentially. The endo and exo isomers are both produced with the cyclobutanone ring in the co-folded in conformation. Computational results support the analysis of the BBAH based mechanism in agreement with experimental results.
期刊介绍：
Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.
京公网安备 11010802042870号
京ICP备2023020795号-1
分享
求助内容：
应助结果提醒方式：
扫码关注我们
