{"title":"On the rearrangement of <i>N</i>-aryl-<i>N</i>-Boc-phosphoramidates to <i>N</i>-Boc-protected <i>o</i>-aminoarylphosphonates.","authors":"Edyta Kuliszewska, Friedrich Hammerschmidt","doi":"10.1007/s00706-017-2058-x","DOIUrl":null,"url":null,"abstract":"<p><strong>Abstract: </strong>Various arylamines were converted in two steps to <i>N</i>-Boc-<i>N</i>-arylphosphoramidates. LiTMP and LDA induced directed <i>ortho</i>-metalation at temperatures from -78 to 0 °C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the nitrogen to the <i>ortho</i>-carbanionic carbon atom gave <i>N</i>-Boc-protected <i>o</i>-aminoarylphosphonates. The nature of the substituent of 3-substituted phenylphosphoramidates strongly influenced the regioselectivity of phosphonate formation. A crossover experiment with a deuterated phosphoramidate proved the intramolecular course of the rearrangement. Three representative <i>N</i>-Boc-<i>o</i>-aminoarylphosphonates were deprotected to access the corresponding <i>o</i>-aminoarylphosphonic acids.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 1","pages":"87-98"},"PeriodicalIF":1.7000,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2058-x","citationCount":"3","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Monatshefte Fur Chemie","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00706-017-2058-x","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2017/12/1 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 3
Abstract
Abstract: Various arylamines were converted in two steps to N-Boc-N-arylphosphoramidates. LiTMP and LDA induced directed ortho-metalation at temperatures from -78 to 0 °C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the nitrogen to the ortho-carbanionic carbon atom gave N-Boc-protected o-aminoarylphosphonates. The nature of the substituent of 3-substituted phenylphosphoramidates strongly influenced the regioselectivity of phosphonate formation. A crossover experiment with a deuterated phosphoramidate proved the intramolecular course of the rearrangement. Three representative N-Boc-o-aminoarylphosphonates were deprotected to access the corresponding o-aminoarylphosphonic acids.
期刊介绍：
"Monatshefte für Chemie/Chemical Monthly" was originally conceived as an Austrian journal of chemistry. It has evolved into an international journal covering all branches of chemistry. Featuring the most recent advances in research in analytical chemistry, biochemistry, inorganic, medicinal, organic, physical, structural, and theoretical chemistry, Chemical Monthly publishes refereed original papers and a section entitled "Short Communications". Reviews, symposia in print, and issues devoted to special fields will also be considered.
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