光延反应机理 光延反应.docVIP

光延反应机理 光延反应 导读：就爱阅读网友为您分享以下“光延反应”的资讯，希望对您有所帮助，感谢您对92的支持! 3754J.Org.Chem.1997,62,3754-3757 NewSynthesisofSubstituted Benzylamines.NovelApplicationofthe MitsunobuReactionToConvertSubstitutedBenzylAlcoholstoAmines? ShamS.Nikam,*BrianE.Kornberg,and MichaelF.Rafferty DepartmentofChemistry,Parke-DavisPharmaceuticalResearchDivision,Warner-LambertCompany,2800 PlymouthRoad,AnnArbor,Michigan48105 ReceivedSeptember10,1996 Introduction SynthesisofaminesfromalcoholsusingtheMitsunobureactioniswell-documented.1Inmostcases,forthesuccessofthereactionitisimportanttohaveprotectedaminesastheacidiccomponent(pKaintheformofamides,2phthalimides,～38)Nof-alkylsulfona-thereactionmides,4N-methyltrifluoromethanesulfonamides,5orhy-drazoicacid6whichundergodeprotonationtogeneratethereactivenucleophile.TheyieldsarehigherwithlowerpKaoftheaminecomponent.Themechanismofthisconversionhasbeenthetopicofinvestigationforseveralyearsandtheonethatbestexplainsthistrans-formationinvolvestheinitialformationofaquaternaryphosphoniumsaltbyadditionofPPh3todiethylazodi-carboxylate(DEAD)followedbyprotonationofthesaltbythesubstitutedaminemoiety(Scheme1).1Theresultingcomplexreactswiththealcoholtogivethealkoxyphosphoniumsalt,whichundergoesanSN1orSN2typedisplacementtogivethedesiredamines.Thus,thisprocessessentiallyprecludestheuseofvariousbasicsecondaryaminesastheaminecomponenttosynthesizetertiaryamines.ThereareveryfewexamplesintheliteraturewheretheMitsunobureactionhasbeenusedtoformsubstitutedamines,especiallybenzylicamines,byreactingalcoholswithsecondaryamineswithpKahigherthan8.Intworeports7,8anintramolecularMitsunobureactionbetweenbenzylicaminoalcoholsyieldedcyclicamineswithdefinedaminesubstituents,whichconsiderablynarrowedthescopeofthereaction.Recently,9Mitsunobu-mediatedintramolecularcycliza-tionofbenzylamineshasbeencarriedoutusingavarietyofazodicarboxamides.However,fromthisstudyitisevidentthatthereareseverallimitationsforthesuccessofthisreaction.Inoneofourongoingprojects,wehaveaneedforavarietyofsecondaryandtertia