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TheMitsunobureactions1ContentsAWhirlwindTourofCurrentMitsunobuChemistry

1.AlcoholInversions2.OtherNucleophiles3.Carbon-CarbonBondFormation4.AlternativeReagents-AzodicabonylPortion5.AlternativeReagents-Trisubstituted

PhosphinePortion6.SomeAlternativestoMitsunbuChemistryReferencesAcknowledgements2AlcoholInversionmechanism3AlcoholInversionWhenasecondaryalcoholsubstratewasused,theesterificationreactionwasshowntoproceedwithanetinversionofstereochemi-stryatthealcoholcarbon.4AlcoholInversionIncaseswherenonucleophilewasaddedtothereactionmixture,orwhenthebetainewasnotabletoabstracttheprotonofthenucleophilicprecursor(pKa>13),thehydrazineportionofthereagentwasshowntoreactwiththealcoholsubstrate(Scheme3)5AlcoholInversion-IntermolecularThealcoholinversionandhydrolysisproceduremaybeeasilycarriedoutinthepresenceofsensitivefunctionality(scheme5)6Alcohol

InversionsSmithandcoworkers7Alcohol

Inversions1991,EliLillychemistsMartinandDodge8Alcohol

InversionsPNBAwasalsousefulinpreventingtheeliminationsidereaction.9Alcohol

InversionsTsunodaandcoworkersfoundthattheuseofTMADandBu3Pwasmoretolerantofstericallycongestedalcohols,resultinginconsistentlybetteryieldsthanthePPh3/DEAD10Alcohol

InversionsTheMitsunobureactionhasalsoenteredtheareaofsolid-phasesynthesis.11AlcoholInversion-IntramolecularSynthesisoflactones,avaluableprecursortoaminoacids12Alcohol

InversionsSynthesisofbis-lactones13Alcohol

InversionsOtherOxygenNucleophiles14Alcohol

Inversionscyclizations15Alcohol

InversionsTheuseofTMADwasshowntoenhancethereactivityofthesenucleophilesoflargerpKa,leadingtohigheroverallyields16Alcohol

InversionsN-hydroxyphthalimidewasalsoanexcellentnucleo-philefortheinthemolecularMitsunobureaction17Alcohol

InversionsOximesserveasoxygennucleophiles18Alcohol

InversionsPreparationofsulfonates19Preparationofsulfonates20OthernucleophilesNitrogenNucleophilesSulfonamidesasNucleophiles21OthernucleophilesApplication1-thesynthesisofnaturalproductSarainA22OthernucleophilesApplication2-thesynthesisofBoc-protectedaminesoraminehydrochloride.23OthernucleophilesApplication3-Nitroarylsulfonamidesasgoodleavingmoiety.24OthernucleophilesOtherapplicationsFmocprotectedsulfonamidesAmidesandImidesasnucleophiles25OthernucleophilesHydroxylaminesasnucleophiles26OthernucleophilesProvideapropargylhydrazine27OthernucleophilesThepreparationofguanidines.28Othernucleophiles

Twomethodoftheformationofazide29OthernucleophilesSynthesisoflysineandarginineanalogs30OthernucleophilesSecondaryandtertiarybenzylamineswithactivatedarylsubstrates31OthernucleophilesSulfurnucleophilesthioester32OthernucleophilesArylthiolsasnucleophiles33OthernucleophilesHalogenationsSynthesisofthealkylhalogens34OthernucleophilesSynthesisoftheintermediateofthemarinenaturalproductsastinsA,BandC35OthernucleophilesZnCl2ascatalyst36Carbon-CarbonBond

FormationsLithiumcyanideasnucleophilesLimitation:primaryalcoholsandstericallyunencumberedsecondarysubstrates37Carbon-CarbonBondFormationsMethanetricarboxylateasnucleophile38Carbon-CarbonBondFormationsC-alkylationofmonosubstitutedMeldrum’sacids39Carbon-CarbonBondFormationsPreparationof-nitrocyclopropanes40Carbon-CarbonBondFormationsDHADandBu3PwereeffectiveforthedeprotonationofactivatedmethylenesubstrateswithlargepKa41AlternativeReagents-AzodicarbonylPortionDEADandADDPThereactivity:DEAD=DIAD<ADDP<TMAD<DHAD42AlternativeReagents-TrisubstitutedPortion43AlternativeReagents-TrisubstitutedPortionDPPE:greatpolartyoftheresultingbis-phosphineoxidebyproduct.---insoluble,removedbyfiltration.Bu3PO:watersolublePh2Py:watersoluble44AlternativeReagents-TrisubstitutedPortion45AppendixofAbbreviations&AcronymsPNBA-p-NitrobenzoicAcidDPPA-diphenylphosphorylazideDEAD-DiethylAzodicarboxylateDIAD-DiisopropylAzodicarboxylateDMAD-DimethylAzodicarboxylateADDP-1,1'-(Azodicarbonyl)dipiperidineTMAD-N,N,N',N',-TetramethylazocarboxamideDHTD-4,7-Dimethyl-3,5,7-henxahydro-1,2,4,7-tetrazocin-3,8-dione46DAP-DP-(p-Dimethylaminophenyl)diphenylphosphineDPPE-1,2-Bis(diphenylamino)phosphinetris-DAP-tris(dimethylamino)phosphineCMMP-CyanomethyltrimethylphosphoraneCMBP-Cyanomethyltributylphosphorane47References1.Mitsunobu,O.;Yamada,M.;Mukaiyama,T.Bull.Chem.Soc.Jpn.1967,40,935.2.Mitsunobu,O.;Eguchi,M.Bull.Chem.Soc.Jpn.1971,44,3427.3.Mitsunobu,O.Synthesis1981,1.4.Hughes,D.L.“TheMitsunobuReaction,”O(jiān)rganicReactions;JohnWiley&Sons,Ltd,1992,vol.42,p.335.5.Hughes,D.L.Org.Pre.Proceed.Int.1996,28,127.6.Mitsunobu,O.“Triphenylphos

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