{"title":"Theoretical studies on the mechanism of Rh-catalyzed [(3+2+2)] cycloisomerization reactions of dienophile-substituted alkylidenecyclopropanes","authors":"Wanjun Zhao, Huimin Xu, Ying Ren, Tingting Zhang, Jianfeng Jia, Hai-Shun Wu","doi":"10.1016/j.mcat.2025.115055","DOIUrl":null,"url":null,"abstract":"<div><div>The detailed reaction mechanism of Rh-catalyzed [(3+2+2)] cycloisomerization reactions of dienophile-substituted alkylidenecyclopropanes to construct the bridged tricyclic products with DFT calculations has been investigated. The catalytic cycle primarily comprises four steps: oxidative addition, proximal alkene insertion, distal alkene insertion, and reductive elimination. The reactions initiate with Rh-mediated the cleavage of cyclopropane distal C−C bond to give the key <em>η</em><sup>4</sup>-TMM Rh(III) intermediate, which undergoes the proximal alkene insertion step to dictate the stereochemical outcome. The subsequent competing the 1,2-insertion and 2,1-insertion of the distal alkene moiety has also been discussed for comparison. The calculations reproduce quite well diastereoselectivity observed experimentally, demonstrating that the <em>cis</em> coordination pathway has high diastereocontrol. For comparison, various C−C coupling reaction pathways and substrate scopes have been examined.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115055"},"PeriodicalIF":3.9000,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Molecular Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S246882312500241X","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The detailed reaction mechanism of Rh-catalyzed [(3+2+2)] cycloisomerization reactions of dienophile-substituted alkylidenecyclopropanes to construct the bridged tricyclic products with DFT calculations has been investigated. The catalytic cycle primarily comprises four steps: oxidative addition, proximal alkene insertion, distal alkene insertion, and reductive elimination. The reactions initiate with Rh-mediated the cleavage of cyclopropane distal C−C bond to give the key η4-TMM Rh(III) intermediate, which undergoes the proximal alkene insertion step to dictate the stereochemical outcome. The subsequent competing the 1,2-insertion and 2,1-insertion of the distal alkene moiety has also been discussed for comparison. The calculations reproduce quite well diastereoselectivity observed experimentally, demonstrating that the cis coordination pathway has high diastereocontrol. For comparison, various C−C coupling reaction pathways and substrate scopes have been examined.
期刊介绍:
Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are:
Heterogeneous catalysis including immobilized molecular catalysts
Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis
Photo- and electrochemistry
Theoretical aspects of catalysis analyzed by computational methods