{"title":"Dimethoxyacetaldehyde-<i>N</i>-triftosylhydrazone: Preparation and Carbene Reactivity in Cyclopropanation and Doyle-Kirmse Reactions.","authors":"Yifan Zhang, Shuang Li, Hongzhu Chen, Wei Song, Yongquan Ning, Zeyun Liu, Yong Wu, Karunanidhi Murali, Paramasivam Sivaguru, Xiaolong Zhang","doi":"10.1021/acs.orglett.5c00223","DOIUrl":null,"url":null,"abstract":"<p><p>Herein, we developed the new, powerful, and easy-to-handle chemical reagent, dimethoxyacetaldehyde-<i>N</i>-triftosylhydrazone (DMHz-Tfs), as a convenient in situ source of dimethoxydiazoethane under mild conditions. We demonstrate the carbene reactivity of DMHz-Tfs in iron-catalyzed cyclopropanation and Doyle-Kirmse reactions, providing access to diverse acetal functionalized cyclopropanes and homoallylic- and allenyl-sulfides at gram-scale with high stereoselectivity. DFT calculations elucidated the involvement of the most stable doublet spin state iron-carbene intermediate over other possible spin states.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":"1941-1948"},"PeriodicalIF":5.0000,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Letters","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.orglett.5c00223","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/2/20 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
Herein, we developed the new, powerful, and easy-to-handle chemical reagent, dimethoxyacetaldehyde-N-triftosylhydrazone (DMHz-Tfs), as a convenient in situ source of dimethoxydiazoethane under mild conditions. We demonstrate the carbene reactivity of DMHz-Tfs in iron-catalyzed cyclopropanation and Doyle-Kirmse reactions, providing access to diverse acetal functionalized cyclopropanes and homoallylic- and allenyl-sulfides at gram-scale with high stereoselectivity. DFT calculations elucidated the involvement of the most stable doublet spin state iron-carbene intermediate over other possible spin states.
在此，我们开发了一种新的，强大的，易于操作的化学试剂，二甲氧基乙醛- n -三甲基腙（DMHz-Tfs），作为二甲氧基重氮乙烷在温和条件下的原位来源。我们证明了DMHz-Tfs在铁催化的环丙烷化和Doyle-Kirmse反应中的碳反应性，提供了在克尺度上具有高立体选择性的多种缩醛功能化环丙烷和均烯丙基和烯丙基硫化物的途径。DFT计算阐明了最稳定的双重自旋态铁-碳烯中间体对其他可能自旋态的参与。
期刊介绍：
Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.
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