DedicatedTo: 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 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–9/28 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–10/28 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 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–11/28 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 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–12/28 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 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–13/28 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–14/28 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 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–15/28 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 SoS–pgp.ToCVol08b.3d–2005-11-26–Ziegler+M(cid:2)ller,K(cid:3)Furt–16/28