Table Of Content

AdditionReactionswithUnsaturatedHydrocarbons Addition Reactions with Unsaturated Hydrocarbons Ruimao Hua Author AllbookspublishedbyWILEY-VCHarecarefully produced.Nevertheless,authors,editors,and Prof.RuimaoHua publisherdonotwarranttheinformation TsinghuaUniversity containedinthesebooks,includingthisbook, DepartmentofChemistry tobefreeoferrors.Readersareadvisedtokeep 30ShuangQingLu inmindthatstatements,data,illustrations, HaidianDistrict proceduraldetailsorotheritemsmay 100084Beijing inadvertentlybeinaccurate. China LibraryofCongressCardNo.:appliedfor CoverImage:©Sebastian Duda/Shutterstock,Reaction BritishLibraryCataloguing-in-PublicationData equationrecreatedbyWiley Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Bibliographicinformationpublishedbythe DeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhis publicationintheDeutscheNationalbiblio- grafie;detailedbibliographicdataareavailable ontheInternetat<http://dnb.d-nb.de>. ©2022WILEY-VCHGmbH,Boschstr.12, 69469Weinheim,Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopartof thisbookmaybereproducedinanyform–by photoprinting,microfilm,oranyothermeans– nortransmittedortranslatedintoamachine languagewithoutwrittenpermissionfromthe publishers.Registerednames,trademarks,etc. usedinthisbook,evenwhennotspecifically markedassuch,arenottobeconsidered unprotectedbylaw. PrintISBN: 978-3-527-34189-4 ePDFISBN: 978-3-527-80483-2 ePubISBN: 978-3-527-80482-5 oBookISBN: 978-3-527-80480-1 Typesetting Straive,Chennai,India Printedonacid-freepaper 10 9 8 7 6 5 4 3 2 1 v Contents Preface ix Acknowledgments xv Abbreviations xvii 1 DimerizationofAlkynesandAlkenes 1 1.1 MarkovnikovDimerizationofTerminalAlkynes 1 1.2 Anti-Markovnikov(Head-to-Head)DimerizationofTerminalAlkynes 7 1.3 DimerizationandCross-dimerizationofTerminalAlkenes 14 1.4 Cross-dimerizationofDifferentAlkynesorAlkyneswithAlkenes 18 References 26 2 AdditionofC(sp)—HBondstoUnsaturatedCompounds 33 2.1 AdditionofTerminalAlkynestoCarbonylCompounds 33 2.2 AdditionofTerminalAlkynestoAlkenes 36 2.3 AdditionofTerminalAlkynestoImines 38 2.4 AdditionofTerminalAlkynestoOtherCompounds 40 References 42 3 FunctionalizedAlkenesfromHydrofunctionalization ofAlkynes 47 3.1 HydroborationsofAlkynes 47 3.2 HydrosilylationofAlkynes 52 3.3 HydrostannationofAlkynes 57 3.4 HydroaminationofAlkynes 61 3.4.1 HydroaminationofAlkyneswithPrimaryAmines 61 3.4.2 HydroaminationofAlkyneswithSecondaryAmines 63 3.4.3 CyclohydroaminationofAlkynes 65 3.4.4 AminocarbonylationofAlkynes 67 3.5 HydrophosphinationofAlkynesandRelatedH—P(O)Addition 69 3.5.1 HydrophosphinationofAlkynes 70 3.5.2 AdditionofPV(O)—HBondtoAlkynes 72 3.6 HydrothiolationofAlkynes 76 3.6.1 MarkovnikovHydrothiolationofAlkynes 77 vi Contents 3.6.2 Anti-MarkovnikovHydrothiolationofAlkynes 78 3.7 AdditionofO-nucleophilestoAlkynes 81 3.7.1 AdditionofAlcoholsandPhenolstoAlkynes 81 3.7.2 AdditionofAcidstoAlkynes 84 References 86 4 HydrofunctionalizationofCarbon–CarbonDoubleBonds 103 4.1 HydroborationofAlkenes 103 4.1.1 MarkovnikovHydroborationofAlkenes 104 4.1.2 Anti-MarkovnikovHydroborationofAlkenes 104 4.1.3 HydroborationofAllenesand1,3-dienes 105 4.1.4 AsymmetricHydroborationofAlkenes 106 4.2 HydrosilylationofCarbon–CarbonDoubleBonds 107 4.2.1 MarkovnikovandAnti-MarkovnikovHydrosilylationofAlkenes 107 4.2.2 HydrosilylationofAllenes 109 4.2.3 Hydrosilylationof1,3-dienes 110 4.2.4 AsymmetricHydrosilylationofAlkenes 110 4.3 HydrostannationofCarbon–CarbonDoubleBonds 111 4.4 HydroaminationofCarbon–CarbonDoubleBonds 113 4.4.1 MarkovnikovHydroaminationofAlkenes 113 4.4.2 Anti-MarkovnikovHydroaminationofAlkenes 115 4.4.3 HydroaminationofAllenesand1,3-dienes 116 4.4.4 AsymmetricHydroaminationofAlkenes 118 4.4.5 NitrogenHeterocyclesfromIntramolecularHydroaminationof Alkenes 119 4.5 HydrophosphinationofAlkenesandRelatedPV(O)—HAddition 121 4.6 HydrothiolationofCarbon–CarbonDoubleBonds 125 4.7 AdditionofO-nucleophilestoAlkenes 128 References 130 5 DoubleFunctionalizationofAlkynesandAlkenesbyAddition ofElement–ElementBonds 147 5.1 AdditionReactionofGroup13Element–ElementBonds 147 5.1.1 cis-AdditionReactionstoAlkynes 147 5.1.2 trans-AdditionReactionstoAlkynes 149 5.1.3 AdditionReactionstoAlkenes 150 5.1.4 Synthesisof1,1-diborylalkanes/AlkenesviaAdditionofB—BBond 151 5.2 AdditionReactionofGroup14Element–ElementBonds 153 5.3 AdditionReactionofGroup15Element–ElementBond 156 5.4 AdditionReactionsofGroup16Element–ElementBond 159 5.4.1 cis-AdditionReactionstoAlkynes 160 5.4.2 trans-AdditionReactionstoAlkynes 161 5.4.3 DifferentHeteroatomBondAdditionReactionstoAlkynes 163 5.4.4 AdditionReactionstoAlkenes 163 Contents vii 5.5 AdditionReactionsofElement–ElementBondsfromDifferentGroup Heteroatoms 164 5.5.1 cis-AdditionReactionstoAlkynes 165 5.5.2 trans-AdditionReactionstoAlkynes 169 5.5.3 AdditionReactionstoAlkenes 172 References 174 6 DoubleFunctionalizationofAlkynesbyAdditionof Carbon–ElementBonds 183 6.1 AdditionReactionsofCarbon–Group13Bonds 183 6.2 AdditionReactionsofCarbon–Group14Bonds 185 6.2.1 AdditionReactionsofCarbon–SiliconBonds 185 6.2.2 AdditionReactionsofCarbon–GermaniumBonds 188 6.2.3 AdditionReactionsofCarbon–TinBonds 189 6.3 AdditionReactionsofCarbon–Group15Bonds 191 6.4 AdditionReactionsofCarbon–Group16Bonds 195 6.4.1 AdditionReactionsofCarbon–OxygenBonds 195 6.4.2 AdditionReactionofCarbon–SulfurBonds 198 6.4.3 AdditionReactionsofCarbon–SeleniumBonds 202 6.5 AdditionReactionsofCarbon–HalogenBondstoAlkynes 204 6.5.1 C(sp3)—XActivationandItsAdditionReactions 205 6.5.2 C(sp2)—XActivationandItsAdditionReactions 208 6.5.3 C(sp)—XActivationandItsAdditionReactions 213 6.6 AdditionReactionsofCarbon–CarbonSingleBonds 216 6.6.1 AdditionReactionsofStrainedC—CBonds 216 6.6.2 AdditionReactionsofC—CNBonds 218 6.6.3 OtherCarbon–CarbonBondCleavageandTheirAddition Reactions 222 References 224 7 CarbocyclesfromAnnulationofAlkynesandAlkenes 235 7.1 Four-MemberedCarbocycles 235 7.1.1 ConstructionofCyclobutenes 235 7.1.2 ConstructionofCyclobutanes 240 7.2 Five-MemberedCarbocycles 242 7.2.1 Five-MemberedCarbocyclesby[2+2+1]Cycloaddition 242 7.2.2 Five-MemberedCarbocyclesby[3+2]Cycloaddition 243 7.2.3 IntramolecularCycloadditionofActivesp3C—HtoCarbon–Carbon UnsaturatedBonds 248 7.2.4 Five-MemberedCarbocyclesfromIntramolecularCycloadditionof UnsaturatedBonds 250 7.3 Six-MemberedCarbocycles 251 7.3.1 BenzeneRingFormation 251 7.3.2 NaphthaleneandPolyaromaticHydrocarbons(PAHs)Ring Formation 258 viii Contents 7.3.3 1,3-CyclohexadieneRingFormationViaCycloadditionofAlkynes 263 7.4 Seven-MemberedCarbocycles 266 7.5 Eight-MemberedandLargerCarbocycles 268 References 272 8 HeterocyclesfromCycloadditionofAlkynes 285 8.1 Four-memberedHeterocycles 285 8.2 Five-memberedHeterocycles 286 8.2.1 Pyrroles,Furans,andThiophenesSynthesis 287 8.2.2 Indoles,Benzo[b]Furans,Benzo[b]Thiophenes,and Benzo[b]Selenophenes 300 8.2.3 Five-memberedRingswithTwoHeteroatoms 308 8.3 Six-memberedHeterocycles 319 8.3.1 PyridineDerivativesviaCycloadditionofAlkyneswithNitriles 320 8.3.2 BenzopyridineDerivatives(QuinolinesandIsoquinolines) 326 8.3.3 2-PyridoneDerivativesandTheirBenzo-derivatives(Quinolinonesand Isoquinolonones) 330 8.3.4 Six-memberedN-heterocyclesHavingTwoNitrogenAtoms 334 8.3.5 2-Pyrone,Coumarin,Isocoumarin,andChromoneDerivatives 336 8.4 OtherHeterocycles 341 References 346 9 CarbonylCompoundsfromAlkynesandAlkenes 365 9.1 HydrationofAlkynes 365 9.2 HydroformylationofAlkynesandAlkenes 369 9.2.1 HydroformylationofAlkynes 369 9.2.2 HydroformylationofAlkenes 370 9.3 HydroacylationofAlkynesandAlkenes 372 9.4 HydroamidationofAlkynesandAlkenes 376 9.5 HydrocarboxylationofAlkynesandAlkenes 378 9.6 HydroesterificationofAlkynesandAlkenes 379 9.7 CarbonylationofAlkynesandAlkenes 380 9.7.1 CarbonylationofAlkynes 381 9.7.2 CarbonylationofAlkenes 384 9.7.3 CyclocarbonylationofAlkynesand/orAlkenes 384 References 393 10 NaturalProductSynthesisviaAlkyneTransformation 407 10.1 HydrofunctionalizationofAlkynesinNaturalProductSynthesis 407 10.2 DoubleFunctionalizationofAlkynesinNaturalProductSynthesis 408 10.3 CycloadditionofAlkynesinNaturalProductSynthesis 408 10.4 CarbonylationofAlkynesinNaturalProductSynthesis 411 References 412 Index 415