{"title":"Stereoselective Intramolecular Oxypalladation of Cyclic 1,3-Dione-Tethered Alkynes","authors":"Lakshmi Revati Magham, Abdus Samad, Anandarao Munakala, Rambabu Chegondi","doi":"10.1021/acs.orglett.5c00106","DOIUrl":null,"url":null,"abstract":"An unconventional, highly stereoselective, and regioselective intramolecular oxypalladation/acyloxylation cascade of alkyne-tethered cyclic 1,3-diones has been developed. This atom-economic Pd(II)-catalyzed annulation reaction is initiated by the oxypalladation of alkyne with an internal carbonyl group via 5-<i>exo</i>-<i>dig</i> cyclization instead of the conventional acetoxypalladation pathway. In this process, the carboxylic acid plays a pivotal role in the generation of an active cationic Pd–complex and the subsequent acyloxylation and proto-demetalation steps. Additionally, this method enables asymmetric cyclization using a chiral bidentate BOX ligand, achieving enantiomeric ratios of ≤93:7.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"30 1","pages":""},"PeriodicalIF":4.9000,"publicationDate":"2025-02-13","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.5c00106","RegionNum":1,"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
An unconventional, highly stereoselective, and regioselective intramolecular oxypalladation/acyloxylation cascade of alkyne-tethered cyclic 1,3-diones has been developed. This atom-economic Pd(II)-catalyzed annulation reaction is initiated by the oxypalladation of alkyne with an internal carbonyl group via 5-exo-dig cyclization instead of the conventional acetoxypalladation pathway. In this process, the carboxylic acid plays a pivotal role in the generation of an active cationic Pd–complex and the subsequent acyloxylation and proto-demetalation steps. Additionally, this method enables asymmetric cyclization using a chiral bidentate BOX ligand, achieving enantiomeric ratios of ≤93:7.
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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