Mátyás Milen, Cintia Bese, Csenge Kovács, András Dancsó, György Keglevich
{"title":"The Addition of α-Hydroxy-benzylphosphonates to Dialkyl Acetylenedicarboxylates; Catalytic Hydrogenation of the Adducts","authors":"Mátyás Milen, Cintia Bese, Csenge Kovács, András Dancsó, György Keglevich","doi":"10.1055/a-2352-7116","DOIUrl":null,"url":null,"abstract":"<p>α-Hydroxy-benzylphosphonates obtained by the Pudovik reaction of substituted benzaldehydes and dialkyl phosphites were added to the triple bond of dialkyl acetylenedicarboxylates. Optimum conditions involved a 24 hours stirring in the presence of 10% diazabicycloundecene in dichloromethane to afford the adducts as a mixture of predominant <i>E</i>- and a minor <i>Z</i>-isomers in 75–90% yields after flash chromatography. The structures of the geometrical isomers were confirmed by NOE- and ROE-measurements. Catalytic hydrogenation of the olefinic moiety of the adducts led to the diastereoisomers of corresponding saturated derivatives.</p>","PeriodicalId":501298,"journal":{"name":"Synthesis","volume":"53 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2024-07-18","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-2352-7116","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
α-Hydroxy-benzylphosphonates obtained by the Pudovik reaction of substituted benzaldehydes and dialkyl phosphites were added to the triple bond of dialkyl acetylenedicarboxylates. Optimum conditions involved a 24 hours stirring in the presence of 10% diazabicycloundecene in dichloromethane to afford the adducts as a mixture of predominant E- and a minor Z-isomers in 75–90% yields after flash chromatography. The structures of the geometrical isomers were confirmed by NOE- and ROE-measurements. Catalytic hydrogenation of the olefinic moiety of the adducts led to the diastereoisomers of corresponding saturated derivatives.
通过取代苯甲醛和二烷基亚磷酸酯的普多维克反应得到的 α-羟基苄基膦酸盐被加入到乙炔二甲酸二烷基酯的三键中。最佳条件是在二氯甲烷中加入 10% 的二氮杂双环庚烷,搅拌 24 小时,然后通过闪速色谱法得到主要为 E 异构体、次要为 Z 异构体的加合物,收率为 75-90%。几何异构体的结构通过 NOE 和 ROE 测量得到了证实。加合物中烯烃分子的催化加氢反应产生了相应饱和衍生物的非对映异构体。