Volume 45b: Aromatic Ring Assemblies, Polycyclic Aromatic Hydrocarbons, and Conjugated ...

32 Pages·2009·0.73 MB·English

VII
Volume 45b:
Aromatic Ring Assemblies, Polycyclic Aromatic
Hydrocarbons, and Conjugated Polyenes
Preface ............................................................... V
TableofContents ..................................................... IX
45.13 ProductClass13:Biaryls
D.A.BlackandK.Fagnou .................................................. 547
45.14 ProductClass14:Arylalkanes
D.A.BlackandK.Fagnou .................................................. 627
45.15 ProductClass15:Poly(phenylenes)
M.AbeandT.Yamamoto .................................................. 653
45.16 ProductClass16:Poly(p-phenylenevinylenes)
L.Pu ...................................................................... 677
45.17 ProductClass17:Poly(xylylenes)
T.Itoh ..................................................................... 697
45.18 ProductClass18:Polystyrenes
F.AldabbaghandO.Gibbons ............................................... 723
45.19 ProductClass19:Naphthalenes,Anthracenes,9H-Fluorenes,andOther
Acenes
S.ToyotaandT.Iwanaga ................................................... 745
45.20 ProductClass20:Cyclobutabenzenes,Biphenylenes,and[N]Phenylenes
S.Toyota .................................................................. 855
45.21 ProductClass21:Phenanthrenes,Helicenes,andOtherAngularAcenes
I.G.Star(cid:2)andI.Star´y ...................................................... 885
45.22 ProductClass22:Pyrenes,Circulenes,andOtherCondensedAcenes
C.-S.ChangandY.-T.Wu ................................................... 955
45.23 ProductClass23:AnnulatedPolycyclicAromaticHydrocarbons
W.-C.LinandY.-T.Wu ...................................................... 1017
45.24 ProductClass24:Pentalenes,s-Indacenes,as-Indacenes,Azulenes,and
Heptalenes,andTheirBenzoDerivatives
K.Abou-HadeedandH.-J.Hansen .......................................... 1043
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VIII Overview
45.25 ProductClass25:ExtendedPolyaromaticHydrocarbons:Graphite,
Fullerene,andCarbonNanotubeSubstructures
I.G.Star(cid:2)andI.Star´y ...................................................... 1115
45.26 ProductClass26:Triphenylenes,Tetraphenylenes,andRelated
Compounds
S.R.WaldvogelandN.Welschoff ........................................... 1147
45.27 ProductClass27:Calixarenes
T.HainoandH.Iwamoto ................................................... 1193
45.28 ProductClass28:MononuclearCyclophanes
T.ShinmyozuandM.Shibahara ............................................ 1267
45.29 ProductClass29:PolynuclearCyclophanes
Y.TobeandT.Takeda ...................................................... 1311
45.30 ProductClass30:ConjugatedPolyenes,IncludingCyclicPolyenesThat
AreNotFullyConjugated
S.Koo ..................................................................... 1349
45.31 ProductClass31:MacromolecularConjugatedPolyenes
T.Masuda,M.Shiotsuki,andF.Sanda ...................................... 1421
KeywordIndex ........................................................... 1441
AuthorIndex ............................................................. 1497
Abbreviations ............................................................. 1535
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IX
Table of Contents
45.13 ProductClass13:Biaryls
D.A.BlackandK.Fagnou
45.13 ProductClass13:Biaryls .................................................. 547
45.13.1 SynthesisofProductClass13 ............................................... 547
45.13.1.1 SynthesisUsingCopperCatalysis ........................................... 547
45.13.1.1.1 Method1: TheUllmannReaction ...................................... 547
45.13.1.1.2 Method2: Cross-CouplingReactions .................................. 549
45.13.1.1.2.1 Variation1: UsingBoronicAcids ........................................ 549
45.13.1.1.2.2 Variation2: UsingOrganotinReagents .................................. 550
45.13.1.2 TheSuzukiCross-CouplingReaction ........................................ 551
45.13.1.2.1 Method1: ArylIodidesinSuzukiCross-CouplingReactions ............. 552
45.13.1.2.2 Method2: ArylBromidesinSuzukiCross-CouplingReactions ........... 555
45.13.1.2.3 Method3: ArylChloridesinSuzukiCross-CouplingReactions ........... 562
45.13.1.2.4 Method4: Aryl4-ToluenesulfonatesandTrifluoromethanesulfonatesin
SuzukiCross-CouplingReactions ........................... 567
45.13.1.2.5 Method5: DiazoniumSaltsinSuzukiCross-CouplingReactions ......... 571
45.13.1.2.6 Method6: SynthesisofHinderedBiarylsUsingtheSuzukiCross-Coupling
Reaction ................................................... 572
45.13.1.2.7 Method7: SynthesisofOligoaromaticsUsingtheSuzukiCross-Coupling
Reaction ................................................... 575
45.13.1.3 TheStilleCross-CouplingReaction .......................................... 577
45.13.1.3.1 Method1: ArylIodidesinStilleCross-CouplingReactions .............. 578
45.13.1.3.2 Method2: ArylBromidesinStilleCross-CouplingReactions ............ 579
45.13.1.3.3 Method3: ArylChloridesinStilleCross-CouplingReactions ............ 580
45.13.1.3.4 Method4: ArylTrifluoromethanesulfonatesinStilleCross-Coupling
Reactions .................................................. 581
45.13.1.3.5 Method5: SynthesisofHinderedBiarylsUsingtheStilleCross-Coupling
Reaction ................................................... 582
45.13.1.4 TheNegishiCross-CouplingReaction ....................................... 584
45.13.1.4.1 Method1: ArylIodidesinNegishiCross-CouplingReactions ............ 584
45.13.1.4.2 Method2: ArylBromidesinNegishiCross-CouplingReactions .......... 586
45.13.1.4.3 Method3: ArylChloridesinNegishiCross-CouplingReactions .......... 587
45.13.1.4.4 Method4: ArylTrifluoromethanesulfonatesinNegishiCross-Coupling
Reactions .................................................. 588
45.13.1.4.5 Method5: SynthesisofHinderedBiarylsUsingtheNegishi
Cross-CouplingReaction ................................... 589
45.13.1.5 TheHiyamaCross-CouplingReaction ....................................... 591
45.13.1.5.1 Method1: ArylIodidesinHiyamaCross-CouplingReactions ............ 591
45.13.1.5.2 Method2: ArylBromidesinHiyamaCross-CouplingReactions ......... 594
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45.13.1.5.3 Method3: ArylChloridesinHiyamaCross-CouplingReactions .......... 596
45.13.1.5.4 Method4: ArylTrifluoromethanesulfonatesinHiyamaCross-Coupling
Reactions .................................................. 598
45.13.1.5.5 Method5: SynthesisofOligoaromaticsUsingtheHiyamaCross-Coupling
Reaction ................................................... 599
45.13.1.6 TheKumada–CorriuCross-CouplingReaction ............................... 599
45.13.1.6.1 Method1: ArylIodidesinKumada–CorriuCross-CouplingReactions .... 599
45.13.1.6.2 Method2: ArylBromidesinKumada–CorriuCross-CouplingReactions .. 601
45.13.1.6.3 Method3: ArylChloridesinKumada–CorriuCross-CouplingReactions .. 602
45.13.1.6.4 Method4: ArylTrifluoromethanesulfonatesandArenesulfonatesin
Kumada–CorriuCross-CouplingReactions .................. 603
45.13.1.6.5 Method5: SynthesisofHinderedBiarylsUsingtheKumada–Corriu
Cross-CouplingReaction ................................... 605
45.13.1.6.6 Method6: SynthesisofOligoaromaticsUsingtheKumada–Corriu
CouplingReaction ......................................... 605
45.13.1.7 DirectArylation ............................................................ 606
45.13.1.7.1 Method1: IntramolecularDirectArylation ............................. 606
45.13.1.7.2 Method2: IntermolecularDirectArylation ............................. 612
45.13.1.7.2.1 Variation1: InthePresenceofDirectingGroups ........................ 612
45.13.1.7.2.2 Variation2: WithoutDirectingGroups .................................. 617
45.13.1.7.3 Method3: Palladium-CatalyzedDomino/CascadeReactionsInvolving
DirectArylation ............................................ 618
45.14 ProductClass14:Arylalkanes
D.A.BlackandK.Fagnou
45.14 ProductClass14:Arylalkanes ............................................. 627
45.14.1 SynthesisofProductClass14 ............................................... 627
45.14.1.1 Method1: Friedel–CraftsAlkylation ................................... 627
45.14.1.1.1 Variation1: UsingAlkylHalides ......................................... 627
45.14.1.1.2 Variation2: UsingAlkenes .............................................. 629
45.14.1.1.3 Variation3: UsingAlcohols ............................................. 632
45.14.1.1.4 Variation4: UsingEsters ............................................... 633
45.14.1.1.5 Variation5: AsymmetricFriedel–CraftsAlkylation ....................... 634
45.14.1.2 Method2: AlkylationofAromaticKetoneswithAlkenesbyC-H
Activation ................................................. 636
45.14.1.3 Method3: AlkylationviaTransition-Metal-CatalyzedCross-Coupling
ReactionswithAlkylElectrophiles .......................... 636
45.14.1.3.1 Variation1: KumadaCross-CouplingReaction ........................... 636
45.14.1.3.2 Variation2: SuzukiCross-CouplingReaction ............................ 638
45.14.1.3.3 Variation3: NegishiCross-CouplingReaction ........................... 639
45.14.1.3.4 Variation4: StilleCross-CouplingReaction .............................. 641
45.14.1.3.5 Variation5: HiyamaCross-CouplingReaction ........................... 641
45.14.1.4 Method4: AlkylationviaTransition-Metal-CatalyzedCross-Coupling
ReactionswithAlkylNucleophiles .......................... 643
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45.14.1.4.1 Variation1: KumadaCross-CouplingReaction ........................... 643
45.14.1.4.2 Variation2: SuzukiCross-CouplingReaction ............................ 644
45.14.1.4.3 Variation3: NegishiCross-CouplingReaction ........................... 647
45.14.1.4.4 Variation4: HiyamaCross-CouplingReaction ........................... 649
45.15 ProductClass15:Poly(phenylenes)
M.AbeandT.Yamamoto
45.15 ProductClass15:Poly(phenylenes) ....................................... 653
45.15.1 ProductSubclass1:LinearPoly(phenylenes) ............................. 653
45.15.1.1 SynthesisofProductSubclass1 ............................................ 654
45.15.1.1.1 Method1: KovacicProcedure ......................................... 654
45.15.1.1.2 Method2: DehalogenativePolycondensationReactionsofDisubstituted
BenzenesUsingNickel(0)Complexes ....................... 655
45.15.1.1.2.1 Variation1: UsingBis(h4-cycloocta-1,5-diene)nickel(0) .................. 656
45.15.1.1.2.2 Variation2: UsingaNickelComplexastheCatalystandZincasthe
ReducingReagent .......................................... 658
45.15.1.1.3 Method3: GrignardCouplingReactions ............................... 659
45.15.1.1.4 Method4: SuzukiCouplingReactions ................................. 661
45.15.1.1.4.1 Variation1: AB-TypeApproach ......................................... 661
45.15.1.1.4.2 Variation2: AA/BB-TypeApproach ...................................... 663
45.15.1.1.5 Method5: StilleCouplingReactions ................................... 664
45.15.1.1.6 Method6: ReactionsUtilizingIntermediatePolymers .................. 666
45.15.1.1.6.1 Variation1: AromatizationbyDecarboxylationofSolublePrecursor
Polymers .................................................. 666
45.15.1.1.6.2 Variation2: DecarboxylationofaPrecursorwithaPoly(p-phenylene)
Backbone .................................................. 668
45.15.1.1.7 Method7: Diels–AlderPolycondensations ............................. 668
45.15.2 ProductSubclass2:MacrocyclicPoly(phenylenes) ....................... 670
45.15.2.1 SynthesisofProductSubclass2 ............................................ 670
45.15.2.1.1 Method1: ReductiveCouplingReactions .............................. 670
45.15.2.1.2 Method2: SuzukiCouplingReactions ................................. 671
45.15.3 ProductSubclass3:DendriticPoly(phenylenes) .......................... 672
45.15.3.1 SynthesisofProductSubclass3 ............................................ 672
45.15.3.1.1 Method1: SuzukiCouplingReactions ................................. 672
45.15.3.1.2 Method2: Diels–AlderCycloadditionReactions ........................ 673
45.16 ProductClass16:Poly(p-phenylenevinylenes)
L.Pu
45.16 ProductClass16:Poly(p-phenylenevinylenes) ............................ 677
45.16.1 ProductSubclass1:UnsubstitutedPoly(p-phenylenevinylenes) .......... 677
45.16.1.1 SynthesisofProductSubclass1 ............................................ 677
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45.16.1.1.1 Method1: PolymerizationofSulfoniumSalts .......................... 678
45.16.1.1.2 Method2: PolymerizationofDithiocarbonates ......................... 679
45.16.1.1.3 Method3: PolymerizationofDithiocarbamates ........................ 679
45.16.1.1.4 Method4: PolymerizationofSulfinylCompounds ...................... 680
45.16.1.1.5 Method5: Ring-OpeningMetathesisPolymerization ................... 681
45.16.2 ProductSubclass2:Substituted,SolublePoly(p-phenylenevinylenes) .... 682
45.16.2.1 SynthesisofProductSubclass2 ............................................ 682
45.16.2.1.1 Method1: PolymerizationofSulfoniumSalts .......................... 683
45.16.2.1.2 Method2: TheGilchMethod .......................................... 683
45.16.2.1.3 Method3: PolymerizationofDithiocarbamates ........................ 685
45.16.2.1.4 Method4: WittigReactions ........................................... 686
45.16.2.1.5 Method5: HornerReactions .......................................... 687
45.16.2.1.6 Method6: HeckCoupling ............................................. 688
45.16.2.1.7 Method7: StilleCoupling ............................................. 689
45.16.2.1.8 Method8: AcyclicDieneMetathesisPolymerization .................... 689
45.16.2.1.9 Method9: Ring-OpeningMetathesisPolymerization ................... 690
45.16.2.1.10 Method10: Polymerizationof(Dichloromethyl)aryls .................... 691
45.16.2.1.11 Method11: McMurryReaction ......................................... 692
45.16.2.1.12 Method12: KnoevenagelCondensation ................................ 692
45.17 ProductClass17:Poly(xylylenes)
T.Itoh
45.17 ProductClass17:Poly(xylylenes) ......................................... 697
45.17.1 ProductSubclass1:Poly(p-xylylenes) .................................... 698
45.17.1.1 SynthesisofProductSubclass1 ............................................ 698
45.17.1.1.1 Method1: Wurtz–FittigDehalogenationof1,4-Bis(halomethyl)arenesin
thePresenceofaMetal .................................... 698
45.17.1.1.2 Method2: Friedel–CraftsCouplingofBenzenewith1,2-Dihaloethanes,
orof(2-Haloethyl)benzenes ................................ 698
45.17.1.1.3 Method3: SynthesisbyIsomerizationPolymerizationofDiazo
Compounds ............................................... 699
45.17.1.1.4 Method4: ReductiveCouplingofAromaticDialdehydes ............... 699
45.17.1.1.5 Method5: PolyrecombinationinthePresenceofPeroxide .............. 700
45.17.1.1.6 Method6: HofmannandHofmann-AnalogousDegradations ........... 700
45.17.1.1.6.1 Variation1: OfTrimethyl(4-methylbenzyl)ammoniumSalts .............. 700
45.17.1.1.6.2 Variation2: OfTrimethyl[4-(trimethylsilylmethyl)benzyl]ammonium
Halides .................................................... 701
45.17.1.1.7 Method7: ElectrochemicalReductionof1,4-Bis(halomethyl)benzenes . 702
45.17.1.1.8 Method8: DehydrohalogenationwithBase ............................ 704
45.17.1.1.8.1 Variation1: Of1-(Halomethyl)-4-methylarenes ......................... 704
45.17.1.1.8.2 Variation2: Of1,4-Bis(halomethyl)arenes ............................... 705
45.17.1.1.8.3 Variation3: Ofp-Xylylenebis(dialkylsulfonium)DihalideSalts ............ 707
45.17.1.1.8.4 Variation4: Of4-(Chloromethyl)benzylSulfoxidesorSulfones ........... 708
45.17.1.1.9 Method9: ChemicalVaporDepositionbyPyrolysis .................... 709
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45.17.1.1.9.1 Variation1: Ofp-Xylenes ............................................... 709
45.17.1.1.9.2 Variation2: OfEstersof1,4-Phenylenedimethanols ..................... 710
45.17.1.1.9.3 Variation3: Of1-(Halomethyl)-or1-(Dihalomethyl)-4-methylbenzenes,or
1,4-Bis(dihalomethyl)benzenes ............................. 711
45.17.1.1.9.4 Variation4: OfCyclophanes ............................................ 712
45.17.1.1.9.5 Variation5: OfaSpiroCompound ...................................... 714
45.17.1.1.10 Method10: Dehalogenationof1,4-Bis(trihalomethyl)benzenesvia
ChemicalVaporDepositionbyPyrolysiswithMetalContact . 714
45.17.2 ProductSubclass2:Poly(m-xylylenes) .................................... 715
45.17.2.1 SynthesisofProductSubclass2 ............................................ 715
45.17.2.1.1 Method1: Wurtz–FittigDehalogenationof1,3-Bis(halomethyl)benzenes
inthePresenceofaMetal .................................. 715
45.17.2.1.2 Method2: ReductiveCouplingofAromaticDialdehydes ............... 716
45.17.3 ProductSubclass3:Poly(o-xylylenes) .................................... 716
45.17.3.1 SynthesisofProductSubclass3 ............................................ 716
45.17.3.1.1 Method1: Wurtz–FittigDehalogenationofa
1,2-Bis(halomethyl)benzeneinthePresenceofaMetal ...... 716
45.17.3.1.2 Method2: ElectrochemicalReductionof1,2-Bis(halomethyl)benzenes . 717
45.17.3.1.3 Method3: Ring-OpeningReactions .................................... 717
45.17.3.1.3.1 Variation1: OfSpiroCompounds ....................................... 717
45.17.3.1.3.2 Variation2: OfBenzocyclobutenes ..................................... 718
45.18 ProductClass18:Polystyrenes
F.AldabbaghandO.Gibbons
45.18 ProductClass18:Polystyrenes ........................................... 723
45.18.1 ProductSubclass1:LinearPolystyrenes .................................. 723
45.18.1.1 SynthesisofProductSubclass1 ............................................ 723
45.18.1.1.1 Method1: ConventionalRadicalPolymerization ....................... 724
45.18.1.1.1.1 Variation1: Addition–FragmentationChainTransfer(AFCT) ............. 725
45.18.1.1.2 Method2: Controlled/LivingRadicalPolymerization(CLRP) ............ 726
45.18.1.1.2.1 Variation1: Nitroxide-MediatedRadicalPolymerization(NMP) .......... 727
45.18.1.1.2.2 Variation2: AtomTransferRadicalPolymerization(ATRP) ............... 728
45.18.1.1.2.3 Variation3: ReversibleAddition–FragmentationChainTransfer(RAFT) ... 729
45.18.1.1.2.4 Variation4: Organotellurium-MediatedLivingRadicalPolymerization
(TERP) ..................................................... 730
45.18.1.1.3 Method3: LivingAnionicPolymerization .............................. 730
45.18.1.1.4 Method4: LivingCationicPolymerization .............................. 731
45.18.1.1.5 Method5: CoordinationPolymerization ............................... 732
45.18.1.1.5.1 Variation1: IsotacticPolymerization .................................... 733
45.18.1.1.5.2 Variation2: SyndiotacticPolymerization ................................ 733
45.18.1.1.6 Method6: ModificationofSubstituents ............................... 734
45.18.1.1.6.1 Variation1: ClickChemistryApproach .................................. 734
45.18.1.1.6.2 Variation2: MiscellaneousOrganicFunctionalGroupTransformations ... 735
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45.18.1.2 ApplicationsofProductSubclass1inOrganicSynthesis ..................... 736
45.18.1.2.1 Method1: SolublePolystyreneSupportsMadebyControlled/Living
RadicalPolymerization ..................................... 737
45.18.2 ProductSubclass2:BranchedPolystyrenes ............................... 737
45.18.2.1 SynthesisofProductSubclass2 ............................................ 737
45.18.2.1.1 Method1: Alkoxyamine-InitiatedRadicalPolymerization ............... 738
45.18.2.1.2 Method2: Controlled/LivingRadicalCopolymerizationwith
Macromonomers .......................................... 739
45.18.3 ProductSubclass3:Cross-LinkedPolystyrenes ........................... 739
45.18.3.1 SynthesisofProductSubclass3 ............................................ 740
45.18.3.1.1 Method1: SuspensionCopolymerizationofStyrenewithCross-Linking
Monomers ................................................. 740
45.19 ProductClass19:Naphthalenes,Anthracenes,9H-Fluorenes,andOther
Acenes
S.ToyotaandT.Iwanaga
45.19 ProductClass19:Naphthalenes,Anthracenes,9H-Fluorenes,andOther
Acenes .................................................................... 745
45.19.1 ProductSubclass1:Naphthalenes ........................................ 746
45.19.1.1 SynthesisofProductSubclass1 ............................................ 746
45.19.1.1.1 SynthesisbyRing-ClosureReactions ........................................ 746
45.19.1.1.1.1 Method1: FormationofThreeC-CBonds ............................ 747
45.19.1.1.1.1.1 Variation1: Palladium-CatalyzedCyclizationofAlkynesandAlkenes ..... 747
45.19.1.1.1.1.2 Variation2: Palladium-CatalyzedCyclizationofAlkynes ................. 747
45.19.1.1.1.1.3 Variation3: Iridium-CatalyzedCyclization ............................... 748
45.19.1.1.1.1.4 Variation4: Copper-CatalyzedCyclizationofOrganozirconium
Compounds ............................................... 748
45.19.1.1.1.1.5 Variation5: InsertionofaNickel–BenzyneComplex ..................... 749
45.19.1.1.1.2 Method2: FormationofTwoC-CBondswithaC2Unit ................ 750
45.19.1.1.1.2.1 Variation1: Titanium-CatalyzedCyclization ............................. 750
45.19.1.1.1.2.2 Variation2: Palladium-CatalyzedCyclizationofOrganozirconium
Compounds ............................................... 750
45.19.1.1.1.2.3 Variation3: Palladium-CatalyzedCyclizationofVinylandArylIodides .... 751
45.19.1.1.1.2.4 Variation4: Diels–AlderReactionofo-Quinodimethanes ................ 752
45.19.1.1.1.2.5 Variation5: Diels–AlderReactionofOrganotungstenCompounds ....... 753
45.19.1.1.1.2.6 Variation6: ElectrophilicCyclization .................................... 753
45.19.1.1.1.2.7 Variation7: LewisAcidCatalyzedCyclization ............................ 754
45.19.1.1.1.2.8 Variation8: CyclizationofPhosphoniumSaltswithEnolates ............. 755
45.19.1.1.1.3 Method3: FormationofTwoC-CBondswithaC Unit ................ 756
3
45.19.1.1.1.3.1 Variation1: CyclizationwithEnones .................................... 756
45.19.1.1.1.3.2 Variation2: Cyclizationwith3-OxoAcetals .............................. 757
45.19.1.1.1.3.3 Variation3: Cyclizationwith3-OxoDithioacetals ........................ 757
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45.19.1.1.1.3.4 Variation4: CyclizationwithGrignardReagents ......................... 758
45.19.1.1.1.4 Method4: FormationofTwoC-CBondswithaC Unit ................ 759
4
45.19.1.1.1.4.1 Variation1: Diels–AlderReactionwithCyclopentadienones .............. 760
45.19.1.1.1.4.2 Variation2: Diels–AlderReactionwithPyrroles .......................... 760
45.19.1.1.1.4.3 Variation3: Diels–AlderReactionwithFurans ........................... 761
45.19.1.1.1.5 Method5: FormationofOneC-CBondtoaBenzeneRing ............. 763
45.19.1.1.1.5.1 Variation1: Friedel–CraftsAcylation .................................... 764
45.19.1.1.1.5.2 Variation2: Friedel–CraftsAlkylation ................................... 764
45.19.1.1.1.5.3 Variation3: LewisAcidCatalyzedRearrangementof
Vinylidenecyclopropanes ................................... 765
45.19.1.1.1.5.4 Variation4: ElectrophilicCyclizationofAlkynes ......................... 766
45.19.1.1.1.5.5 Variation5: Base-CatalyzedCyclizationofEnynes ....................... 766
45.19.1.1.1.5.6 Variation6: Base-CatalyzedRearrangementofMethylenetetrahydrofurans 767
45.19.1.1.1.6 Method6: FormationofOneC-CBondatOtherSites ................. 768
45.19.1.1.1.6.1 Variation1: BergmanCyclization ....................................... 768
45.19.1.1.1.6.2 Variation2: Tellurium-MediatedCycloaddition .......................... 769
45.19.1.1.1.6.3 Variation3: ReductiveCyclization ...................................... 769
45.19.1.1.1.6.4 Variation4: Ring-ClosingMetathesis .................................... 770
45.19.1.1.1.6.5 Variation5: Metal-CatalyzedCyclization ................................ 770
45.19.1.1.2 SynthesisbyRingTransformation ........................................... 771
45.19.1.1.2.1 Method1: ValenceIsomerism ......................................... 771
45.19.1.1.2.1.1 Variation1: FromDewarBenzenes ..................................... 771
45.19.1.1.2.1.2 Variation2: FromBenzvalenes .......................................... 772
45.19.1.1.2.2 Method2: RearrangementReactions .................................. 772
45.19.1.1.2.2.1 Variation1: Metal-MediatedRingExpansion ............................ 772
45.19.1.1.2.2.2 Variation2: ThermalRingExpansion .................................... 773
45.19.1.1.2.2.3 Variation3: Acid-CatalyzedRingContraction ........................... 773
45.19.1.1.3 SynthesisbyAromatization ................................................ 774
45.19.1.1.3.1 Method1: OxidationofHydrogenatedCompounds .................... 774
45.19.1.1.3.1.1 Variation1: DehydrogenationoverPalladiumonCarbon ................ 774
45.19.1.1.3.1.2 Variation2: DehydrogenationbySulfur ................................. 775
45.19.1.1.3.1.3 Variation3: DehydrogenationbyBenzoquinones ........................ 776
45.19.1.1.3.1.4 Variation4: OtherMethods ............................................ 776
45.19.1.1.3.2 Method2: SynthesisfromTetralonesorNaphthoquinones ............. 777
45.19.1.1.3.2.1 Variation1: DirectConversionintoNaphthalenes ....................... 777
45.19.1.1.3.2.2 Variation2: StepwiseConversionintoNaphthalenes .................... 778
45.19.1.1.3.3 Method3: EliminationReactions ...................................... 779
45.19.1.1.3.3.1 Variation1: Dehydration ............................................... 779
45.19.1.1.3.3.2 Variation2: Dehydrobromination ....................................... 780
45.19.1.1.4 SynthesisbySubstitutionofExistingSubstituents ........................... 780
45.19.1.1.4.1 Method1: SubstitutionofHydrogen .................................. 780
45.19.1.1.4.1.1 Variation1: Friedel–CraftsAlkylation ................................... 780
45.19.1.1.4.2 Method2: SubstitutionofCarbon ..................................... 781
45.19.1.1.4.2.1 Variation1: Dealkylation ............................................... 781
45.19.1.1.4.3 Method3: SubstitutionofHeteroatoms ............................... 782
Science of Synthesis Original Edition Volume 45b
© Georg Thieme Verlag KG
XVI TableofContents
45.19.1.1.4.3.1 Variation1: CouplingwithOrganoboranes .............................. 782
45.19.1.1.4.3.2 Variation2: CouplingwithGrignardReagents ........................... 783
45.19.1.1.4.3.3 Variation3: CouplingwithOrganoaluminumComplexes ................ 784
45.19.1.1.4.3.4 Variation4: CouplingwithOtherOrganometallicReagents .............. 785
45.19.1.1.5 SynthesisbyModificationofSubstituents ................................... 785
45.19.1.1.5.1 Method1: AlkylationofAlkylSubstituents ............................. 785
45.19.1.1.5.2 Method2: DehalogenationofHalomethylGroups ..................... 786
45.19.1.1.5.3 Method3: DeoxygenationofHydroxymethylGroups ................... 787
45.19.1.1.5.4 Method4: ReductionofAcylGroups .................................. 787
45.19.2 ProductSubclass2:Anthracenes ......................................... 788
45.19.2.1 SynthesisofProductSubclass2 ............................................ 788
45.19.2.1.1 SynthesisbyRing-ClosureReactions ........................................ 788
45.19.2.1.1.1 Method1: FormationoftheTwoTerminalBenzeneRings .............. 788
45.19.2.1.1.1.1 Variation1: Palladium-CatalyzedCyclization ............................ 788
45.19.2.1.1.1.2 Variation2: Copper-CatalyzedCyclizationwithOrganozirconium
Compounds ............................................... 789
45.19.2.1.1.1.3 Variation3: Diels–AlderReactionwithFuransandPyrroles .............. 790
45.19.2.1.1.1.4 Variation4: Diels–AlderReactionofBenzo-1,4-quinone ................. 791
45.19.2.1.1.1.5 Variation5: BergmanCyclization ....................................... 792
45.19.2.1.1.2 Method2: FormationoftheCentralBenzeneRingandaTerminal
BenzeneRing .............................................. 793
45.19.2.1.1.3 Method3: FormationoftheCentralBenzeneRing ..................... 794
45.19.2.1.1.3.1 Variation1: Acid-CatalyzedCyclizationofBenzylAcetates ............... 794
45.19.2.1.1.3.2 Variation2: ThermalCyclodehydration ................................. 794
45.19.2.1.1.3.3 Variation3: Acid-CatalyzedCyclizationofKetones ...................... 795
45.19.2.1.1.3.4 Variation4: Acid-CatalyzedCyclizationofAzines ........................ 795
45.19.2.1.1.3.5 Variation5: Diels–AlderReactionofIsobenzofuran ...................... 796
45.19.2.1.1.3.6 Variation6: Diels–AlderReactionofIsoindoles .......................... 797
45.19.2.1.1.4 Method4: SynthesisbyFormationofaTerminalBenzeneRing ......... 798
45.19.2.1.1.4.1 Variation1: Iridium-CatalyzedCyclization ............................... 798
45.19.2.1.1.4.2 Variation2: Diels–AlderReactionofDienes ............................. 798
45.19.2.1.1.4.3 Variation3: BergmanCyclization ....................................... 799
45.19.2.1.2 SynthesisbyRingTransformation ........................................... 800
45.19.2.1.2.1 Method1: RingContractionbyPyrolysis ............................... 800
45.19.2.1.3 SynthesisbyAromatization ................................................ 801
45.19.2.1.3.1 Method1: OxidationofDihydroanthracenes ........................... 801
45.19.2.1.3.1.1 Variation1: DehydrogenationbyConventionalMethods ................ 801
45.19.2.1.3.1.2 Variation2: DehydrogenationviaanAnion .............................. 802
45.19.2.1.3.1.3 Variation3: DehydrogenationbyOxygen ............................... 803
45.19.2.1.3.2 Method2: SynthesisfromOxygenatedCompounds .................... 804
45.19.2.1.3.2.1 Variation1: AlkylationofAnthraquinones ............................... 804
45.19.2.1.3.2.2 Variation2: AlkylationofAnthracen-9(10H)-ones ....................... 805
45.19.2.1.3.2.3 Variation3: ReductionofAnthraquinones .............................. 806
45.19.2.1.3.2.4 Variation4: ReductionofAnthracenones ............................... 807
Science of Synthesis Original Edition Volume 45b
© Georg Thieme Verlag KG