Table Of ContentDedicatedTo:
Allchemistsmesmerizedbythe
utterbeautyofmethyllithiumsparks.
Allthosewhonurtureperseverance
andcollaborationofminds.
Ourparents,ourchildren,andtheirs.
Allstudents,past,present,andfuture.
AndtotheindomitableKristaVoigt.
Science of Synthesis Original Edition Volume 8b
© Georg Thieme Verlag KG
IX
Volume 8:
Compounds ofGroup1 (Li…Cs)
Volume8a
8.1 LithiumCompounds
KeywordIndex
AuthorIndex
Abbreviations
Volume8b
8.2 SodiumCompounds
8.3 PotassiumCompounds
8.4 RubidiumandCesiumCompounds
KeywordIndex
AuthorIndex
Abbreviations
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XI
Volume 8b:
Compounds ofGroup1 (Li…Cs)
Preface ................................................................. V
TableofContents ....................................................... XV
Introduction
M.MajewskiandV.Snieckus ............................................. 863
8.2 ProductClass2:SodiumCompounds
A.MordiniandM.Valacchi ............................................... 879
8.2.1 ProductSubclass1:SodiumMetalandSodium–PotassiumAlloy
P.VenturelloandM.Barbero ............................................. 881
8.2.2 ProductSubclass2:SodiumHydride
P.VenturelloandM.Barbero ............................................. 895
8.2.3 ProductSubclass3:SodiumHalidesandSodiumCyanide
A.PaulKrapcho ......................................................... 925
8.2.4 ProductSubclass4:Sodium–OxygenCompounds
A.Jon´czykandA.Kowalkowska .......................................... 1011
8.2.5 ProductSubclass5:Sodium–NitrogenCompounds
A.Jon´czykandA.Kowalkowska .......................................... 1141
8.2.6 ProductSubclass6:AlkylsodiumCompounds
A.MordiniandM.Valacchi ............................................... 1197
8.2.7 ProductSubclass7:AlkenylsodiumCompounds
A.MordiniandM.Valacchi ............................................... 1205
8.2.8 ProductSubclass8:SodiumAcetylides
A.MordiniandM.Valacchi ............................................... 1209
8.2.9 ProductSubclass9:AllylsodiumCompounds
A.MordiniandM.Valacchi ............................................... 1215
8.2.10 ProductSubclass10:ArylsodiumCompoundsand
SodiumCyclopentadienide
A.MordiniandM.Valacchi ............................................... 1221
8.2.11 ProductSubclass11:BenzylsodiumCompounds
A.MordiniandM.Valacchi ............................................... 1227
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XII Overview
8.2.12 ProductSubclass12:1,1-DisubstitutedOrganosodiumCompounds
R.Ła´zny ................................................................. 1231
8.2.13 ProductSubclass13:1-MonosubstitutedOrganosodiumCompounds
R.Ła´zny ................................................................. 1241
8.2.14 ProductSubclass14:Æ-SodiocarboxylicAcidsand
RelatedSodiumCompounds
E.Juaristi,O.Mu(cid:4)oz-Mu(cid:4)iz,andR.Melgar-Fern(cid:5)ndez ...................... 1259
8.2.15 ProductSubclass15:Æ-SodioAldehydes,Æ-SodioKetones,
andRelatedCompounds
E.JuaristiandR.Melgar-Fern(cid:5)ndez ....................................... 1285
8.3 ProductClass3:PotassiumCompounds
M.J.White .............................................................. 1297
8.3.1 ProductSubclass1:PotassiumMetal
P.VenturelloandM.Barbero ............................................. 1299
8.3.2 ProductSubclass2:PotassiumHydride
P.VenturelloandM.Barbero ............................................. 1315
8.3.3 ProductSubclass3:PotassiumHalides,PotassiumCyanide,
andPotassiumCarbonate
J.V.Comasseto,R.L.O.R.Cunha,andC.C.Silveira ....................... 1345
8.3.4 ProductSubclass4:PotassiumHydroxideandPotassiumAlkoxides
P.VenturelloandM.Barbero ............................................. 1361
8.3.5 ProductSubclass5:Potassium–Sulfur,–Selenium,
and–TelluriumCompounds
J.V.Comasseto,R.L.O.R.Cunha,andC.C.Silveira ....................... 1387
8.3.6 ProductSubclass6:PotassiumAmidesandPhosphides
P.VenturelloandM.Barbero ............................................. 1399
8.3.7 ProductSubclass7:OrganometallicCompoundsofPotassium
A.MordiniandM.Valacchi ............................................... 1437
8.4 ProductClass4:RubidiumandCesiumCompounds
A.Streitwieser ........................................................... 1475
8.4.1 ProductSubclass4:RubidiumandCesiumMetals
A.StreitwieserandF.Hasanayn ........................................... 1477
8.4.2 ProductSubclass2:RubidiumandCesiumHalides
R.M.Kellogg ............................................................ 1485
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Overview XIII
8.4.3 ProductSubclass3:RubidiumandCesiumCarbonates
R.M.Kellogg ............................................................ 1497
8.4.4 ProductSubclass4:OrganometallicCompoundsofRubidiumand
Cesium
A.StreitwieserandL.Xie ................................................. 1517
KeywordIndex ....................................................... 1529
AuthorIndex ........................................................... 1567
Abbreviations .......................................................... 1611
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XV
Table of Contents
Introduction
M.MajewskiandV.Snieckus
Introduction ............................................................. 863
8.2 ProductClass2:SodiumCompounds
A.MordiniandM.Valacchi
8.2 ProductClass2:SodiumCompounds .................................... 879
8.2.1 ProductSubclass1:SodiumMetalandSodium–PotassiumAlloy
P.VenturelloandM.Barbero
8.2.1 ProductSubclass1:SodiumMetalandSodium–PotassiumAlloy ......... 881
ApplicationsofProductSubclass1inOrganicSynthesis .................... 881
8.2.1.1 Method1: ReductionofCarbon-HeteroatomMultipleBonds .......... 881
8.2.1.1.1 Variation1: KetoneReductioninProticConditions ..................... 882
8.2.1.1.2 Variation2: KetoneReductioninLiquidAmmonia ...................... 883
8.2.1.1.3 Variation3: BimolecularReductionofCarbonylGroups(PinacolCoupling) 883
8.2.1.1.4 Variation4: ReductionofEsters ....................................... 884
8.2.1.1.5 Variation5: ReductionofAmides ...................................... 885
8.2.1.1.6 Variation6: ReductionofEnones ...................................... 886
8.2.1.1.7 Variation7: ReductionofNitriles ...................................... 887
8.2.1.1.8 Variation8: Reductionof1,3-Diimines ................................. 887
8.2.1.2 Method2: ReductionofC-CMultipleBonds .......................... 887
8.2.1.2.1 Variation1: HydrogenationofC=CBonds .............................. 887
8.2.1.2.2 Variation2: HydrogenationofAlkynes ................................. 889
8.2.1.3 Method3: ReductionofCarbon-HeteroatomSingleBonds ............ 889
8.2.1.3.1 Variation1: DehalogenationofAlkylHalides ........................... 889
8.2.1.3.2 Variation2: CleavageofEstersandEthers .............................. 890
8.2.1.3.3 Variation3: CleavageofC-SBonds .................................... 891
8.2.1.4 Method4: ReductionofC-CSingleBonds ............................ 892
8.2.1.4.1 Variation1: Decyanation .............................................. 892
8.2.2 ProductSubclass2:SodiumHydride
P.VenturelloandM.Barbero
8.2.2 ProductSubclass2:SodiumHydride ..................................... 895
SynthesisofProductSubclass2 ........................................... 895
8.2.2.1 Method1: PreparationofSodiumHydride ............................ 895
ApplicationsofProductSubclass2inOrganicSynthesis .................... 896
8.2.2.2 Method2: MetalationoftheHydroxyGroup .......................... 896
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XVI TableofContents
8.2.2.2.1 Variation1: EtherificationinthePresenceof15-Crown-5 ................ 896
8.2.2.2.2 Variation2: EtherificationwithSuperactiveSodiumHydride ............ 897
8.2.2.2.3 Variation3: EtherificationonSolidSupport ............................. 897
8.2.2.2.4 Variation4: Base-PromotedCyclizationofHydroxyPropargylicSulfones 898
8.2.2.2.5 Variation5: FormationofHighlySubstitutedDiphenylCarbonates ...... 899
8.2.2.3 Method3: AlkylationofAminesandAmides .......................... 900
8.2.2.3.1 Variation1: TransformationofDihydroimidazolesinto
2,4,6-TrisubstitutedPyrimidines ........................... 901
8.2.2.4 Method4: MetalationofC-HGroups ................................ 902
8.2.2.4.1 Variation1: TrappingofÆ-LactamsbyWeakNuclephiles ................ 902
8.2.2.4.2 Variation2: SynthesisofYlides ........................................ 903
8.2.2.4.3 Variation3: Base-PromotedCyclizationofAlkynones ................... 905
8.2.2.4.4 Variation4: DieckmannCondensation ................................. 905
8.2.2.4.5 Variation5: TheDarzensReaction ..................................... 906
8.2.2.4.6 Variation6: Synthesisofª-OxoAcids .................................. 906
8.2.2.4.7 Variation7: Synthesisof1,3-Diketones ................................. 907
8.2.2.4.8 Variation8: TandemMichael–DieckmannSynthesisofCarbocycles ...... 908
8.2.2.4.9 Variation9: DoubleAnnulationLeadingtoFusedBicyclicCompounds ... 908
8.2.2.4.10 Variation10: Æ-AlkylationofSulfones ................................... 909
8.2.2.4.11 Variation11: RegiocontrolledSyntheticApproachto
UnsymmetricalKetones ................................... 910
8.2.2.4.12 Variation12: AllylationofAlkenylidenemalonate ........................ 911
8.2.2.4.13 Variation13: Base-InducedCycloaddition ............................... 912
8.2.2.4.14 Variation14: AsymmetricAdditionofMalonateNucleophiles ............ 912
8.2.2.4.15 Variation15: CyclizationofPhenylacetonitriles .......................... 913
8.2.2.5 Method5: ReductionofCarbon-HeteroatomMultipleBonds .......... 914
8.2.2.5.1 Variation1: ReductionofTosylhydrazones ............................. 914
8.2.2.5.2 Variation2: ReductionUsingMetal-ContainingComplexReducingAgents 914
8.2.2.6 Method6: ReductionofC-CMultipleBonds .......................... 917
8.2.2.7 Method7: ReductionofSilylDerivatives .............................. 918
8.2.2.8 Method8: ReductionofCarbon-HeteroatomSingleBonds ............ 919
8.2.2.9 Method9: EliminationReactions ..................................... 920
8.2.2.9.1 Variation1: Dehydrohalogenation ..................................... 920
8.2.2.9.2 Variation2: DehydrobrominationandDebromination .................. 921
8.2.2.9.3 Variation3: Dehydrosilylationof(cid:2)-Hydroxysilanes ...................... 921
8.2.3 ProductSubclass3:SodiumHalidesandSodiumCyanide
A.PaulKrapcho
8.2.3 ProductSubclass3:SodiumHalidesandSodiumCyanide ................ 925
ApplicationsofProductSubclass3inOrganicSynthesis .................... 925
8.2.3.1 SodiumFluoride .......................................................... 925
8.2.3.1.1 Method1: SynthesisofFluoroCompoundsbySubstitution ............ 925
8.2.3.1.1.1 Variation1: AlkylandCycloalkylFluoridesbyFormalDisplacementof
aHydroxyGroup .......................................... 925
8.2.3.1.1.2 Variation2: FluoromethylEthersfromChloromethylEthers ............. 926
8.2.3.1.1.3 Variation3: PerfluoroEstersbyDirectFluorination ..................... 926
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