Deepak Kumar, Nishikant Satam, Irishi N. N. Namboothiri
{"title":"Magnesium-Mediated Regioselective Additions of Bromoform to Quinone Methides and Aurone-Derived Azadienes","authors":"Deepak Kumar, Nishikant Satam, Irishi N. N. Namboothiri","doi":"10.1055/a-2353-1722","DOIUrl":null,"url":null,"abstract":"<p>The magnesium-mediated addition of bromoform to conjugated electron-deficient alkenes and imines, such as <i>para</i>-quinone methides (<i>p</i>-QMs) and aurone-derived azadienes, respectively, is reported here for the first time. While <i>p</i>-QMs undergo exclusive and hitherto unreported 1,6-addition of bromoform to afford benzylic tribromomethylated diarylmethanes, aurone-derived azadienes undergo both 1,2- and 1,4-additions to furnish α- and γ-tribromomethylamines. A mechanism involving the intermediacy of the tribromomethyl radical has been proposed based on control experiments and EPR studies. Representative synthetic transformations have also been carried out.</p> ","PeriodicalId":501298,"journal":{"name":"Synthesis","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Synthesis","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1055/a-2353-1722","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
The magnesium-mediated addition of bromoform to conjugated electron-deficient alkenes and imines, such as para-quinone methides (p-QMs) and aurone-derived azadienes, respectively, is reported here for the first time. While p-QMs undergo exclusive and hitherto unreported 1,6-addition of bromoform to afford benzylic tribromomethylated diarylmethanes, aurone-derived azadienes undergo both 1,2- and 1,4-additions to furnish α- and γ-tribromomethylamines. A mechanism involving the intermediacy of the tribromomethyl radical has been proposed based on control experiments and EPR studies. Representative synthetic transformations have also been carried out.