1膦酸d核糖類似物的合成

1、◎天洋大謦碩士學(xué)位論文一■K●■■：●爿，：●■●0____學(xué)科專業(yè)：圭塹絲王作者姓名：畦蝎——指導(dǎo)教帥：間蕉壬塑撞廠]工凈肖zⅡ巒生暉ABSTRACTTheglycosylphosphonatesasanaloguesofnaturalphosphates，bearingthecarbonphosphorousbondwhichisincapableofhydrolyzedby“ordinary’phosphatascshaveexc

2、ellentbiologicalactivitiesDesiredproductsinthispaper(dialkyl)1phosphonateDfibosearekeyintermedimesofnmnerousvitalphosphonatcsInordertooptimizethesynthesisandseparationanomafsof1(dialkyl)2，5一anhydroD—riobofuranosylphospho

3、natcsweresynthesizedbyHomerEmmonsl眥tionsinwhichthreedifferentprotectedDfibosederivativeswercusedasthestartingmaterials，respectivelyInrouteOIletheintroductionofphosphonatcmoietyto23一Oisopropylidcne一5OtritylD—ribofuranosew

4、asaccomplishedthroughHorncrEmmons’twophasereactionSeparationofanomc目rsofcarbohydralephosphonateswaslimitedtopreparativeTLCplatesduetotheextremesimilarityoftheirpolaritiesDesiredproductsWq：Teobtainedafterdeproteetionwitht

5、heactionoftrifluroaceticacidwithtotal30％yieldInroutetwo，230isopropyledcne一5OpivaloylDribofiaanosereactedwithtetra刪methlenediphosphonateto#vel(diethyl)一2，3Oisopropyledene5OpivaloylDribofuranosylphosphonateSodiumethoxidewa

6、susedtOrel∞tovethepivaloylgroupThearlomerswereisolatedandthenhydrolyzcdunderacidicconditiontoprovidethedesiredproductsand，averagetotalyieldreachedabout36％InthethirdrolRctheDribose1#osphonatesderivativeswereobtainedthroug

7、hHomcrEmmonsreactionA_f記rseparatingtheanomeIs，anddesiredproductsWel“eobtainedtlⅡoughdeprotectionundertheconditionofPd／CandH2respectivelyTheaveragetotalyieldwasabout40％Wealsotriedthepreparationof(dipivoxil)1phosphonateDfi

8、bofuranoseUnfortunatelyitwasfoundthatneitherthetransesterificationofl(dimethyl)一2，3，5OIribenzyla(13)Dribofuranosephosphonatewithchloromethylpivalate，northeHomerErnmonsreactionofprotectedD—ribose’Sprimaryalcoholwithtetra(

9、pivaloyloxymethyl)methlenediphosphonatecouldaffordthetargetedproductKEYWORDS：naturalphosphates；glycosylIphosphonatcsanalogues；anomcrs；HomerEmmonsreaction；tetraalkylmethlencdiphosphonate；(dipivoxil)lphosphonate—Dribofuran