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7664J.Am.Chem.SOC.1986,108,7664-7678
StereochemistryandMechanismoftheWittigReaction.
DiastereomericReactionIntermediatesandAnalysisofthe
ReactionCourse
BruceE.Maryanoff,*tAllenB.Reitz,?MartinS.Mutter,?RuthR.Inners,+
HaroldR.Almond,Jr.,?RobertR.Whittle,*andR.A.Olofson*
ContributionfromtheChemicalResearchDepartment,McNeilPharmaceutical,SpringHouse,
Pennsylvania19477,andtheDepartmentofChemistry,ThePennsylvaniaStateUniversity,
UniversityPark,Pennsylvania16802.ReceivedFebruary18,I986
Abstract:Individualdiastereomeric1,2-oxaphosphetaneshavebeendirectlyobservedintheWittigolefinationreactionby
useofhigh-fieldNMRspectroscopyatlowtemperature,permittingdetailedevaluationoftheseintermediates.Reactions
ofbenzaldehydewithylide4andwithylide11weremonitoredovertimetogainthefirstintimatekineticperspectiveofthe
Wittigreaction.Completekineticdataarepresented,alongwiththespecificsofouranalysis.Inanumberofinstances,the
reactionofnonstabilizedphosphorusylideswithaldehydesshowedanoncorrespondencebetweentherelativeproportionof
cis-andtrans-oxaphosphetanesatlowtemperature(priortosignificantalkeneformation)andthefinalproportionofZand
Ealkenes,resultinginanexaggeratedproductionofEalkene(aphenomenontermedstereochemicaldriftforconvenience).
Thus,therewasameasu
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