碘催化的有机化学反应

TheApplicationsofIodineasCatalystinOrganicReactionContentTheformationandcleavageofetherbondAcylreactionAdditionreactionOxidationreactionReductivereactionRearrangementreaction碘处于元素周期表第ⅦA族的最下端,具有较大的原子半径和多层电子结构,使它除具有该族元素的通性外,还具有一定的特殊性质,如能催化有机化学反应,因而受到有机化学界的重视醚键的形成和断裂J.Org.Chem.2001,66,7527-7529AConvenientMethodforProtectionandDeprotectionofAlcoholsandPhenolsasAlkylsilylEthersCatalyzedbyIodineUnderMicrowaveIrradiationR-OHR-OSiR3TBDMSCl/TMSClI2,MicrowaveSynth.Commun.,2003,33,4005.2酰化反应在催化量的碘存在下伯、仲、叔醇或酚和乙酐反应也能高收率地得到乙酸酯,在无溶剂条件下反应速度更快,伯、仲醇和酚的酰化在几秒中就可完成。碘甲醇体系在室温能选择性脱保护乙酸芳香酯,乙酸烷基酯不被裂解。苯环上带有强吸电子基团如硝基、醛基、羧酸酯的乙酸芳基酯酯基也不被裂解。TetrahedronLetters47(2006)4065–40681,1-二乙酸酯的生成反应J.Org.Chem.2006,71,8283-8286AdditionTetrahedronLettersPergamon44(2003)3001–3003I2asanefficientcatalystinionicDiels–AlderreactionsofunsaturatedacetalsTetrahedronLetters47(2006)4509–4512Hosomi-SakuraiReaction，allylationJ.Org.Chem.2004,69,4005-4006TetrahedronLetters40(1999)5923-5926Thismethodwasonlysuccessfulwithcyclicallylicacetates.TetrahedronLetters45(2004)6505–6507iodine-catalyzedallylationandalkynylationofcyclicallylicacetatesTetrahedronLetters48(2007)3963–3967TetrahedronLetters48(2007)8120–8124TetrahedronLettersIodine-catalyzedallylationof1,3-dicarbonylcompoundswithallylicalcoholsatroomtemperature+I2CH2Cl2,r.t.,1h,95%Synlett2001,No.10,1638–1640Synthesis2003,No.2,247–250YadavJS,ReddyBVS,ReddyMS.Synlett,2003,(11):1722—1724MichaeladditionWangSY,JiSJ,LohTP.Synlett,2003,(15):2377—2379TetrahedronLetters48(2007)2867–2870TetrahedronLetters47(2006)1889–1893NO2RHNHNRNO2+I2ether,rt.89-99%Tetrahedron61(2005)11751–11757Friedel–CraftsreactionTetrahedronLetters48(2007)6881–6885TetrahedronLetters47(2006)3127–3130Tetrahedron,2004,60:2051—2055TetrahedronLett.,2003,44:1959—1961Moleculariodinecatalyzedsynthesisofaryl-14Hdibenzo[a,j]xanthenesundersolvent-freeconditionBioorganic&MedicinalChemistryLetters17(2007)621–62390-95%JournalofMolecularCatalysisA:Chemical261(2007)180–183Iodinecatalyzedpreparationofamidoalkylnaphtholsinsolutionandundersolvent-freeconditions氧化反应O．L．2006．Vol.8,No.12。2491-2494IodineasaCatalystforEfficientConversionofKetonestogem-DihydroperoxidesbyAqueousHydrogenPeroxideLight-Induced,Iodine-CatalyzedAerobicOxidationofUnsaturatedTertiaryAminesJ.Org.Chem.1990,55,3679-3682AerobicphotocatalyticoxidationofactivatedbenzylicandallylicalcoholstocarbonylcompoundscatalyzedbymoleculariodineTetrahedronLetters47(2006)8953–8957J.Org.Chem.2004,69,5153-5154DMSO/N2H4·H2O/I2/H2O/CH3CN:ANewSystemforSelectiveOxidationofAlcoholsinHydratedMedia还原反应Karimi,B.;Zareyee,D.Synthesis2003,1875.N-BromosuccinimideandIodineCatalyzedHighlyEfficientDeoxygenationofSulfoxidestoThioethersUsing3-MercaptopropionicAcidunderMildReactionConditionsSinghJ,KaurI,KaurJ,etal.Synth.Commun.,2003,33:191—19779-95%SpeedyandRegioselective1,2-ReductionofConjugateda,b-UnsaturatedAldehydesandKetonesUsingNaBH4/I2YanadaR,BesshoK,YanadaK.Synlett,1995,(5):443—444芳香硝基化合物在催化量的碘作用下在THF,NH4Cl水溶液中被钐还原为相应的伯胺双键重排，构型翻转J.Org.Chem.2001,66,8135-8138杂环的合成YadavJS,ReddyBVS,HashimSR.J.Chem.Soc.,PerkinTrans.1,2000,(18):3082—3084Tetrahedron54(I998)13485-13494SNOOClNa+91%Iodine-CatalyzedAziridinationofAlkenesusingChloramine-TasaNitrogenSourceR1R2OHR3OR2R1R3I2/CH2Cl2,r.t.30min,67-98%KimKM,JeonDJ,RyuEK.Synthesis,1998,(6):835—836AConvenientSynthesisof2-Alkyl-2-methyltetrahydrofuransfrom4-Methylalk-4-en-1-olsCatalyzedbyIodineBandgarBP,BettigeriSV,JoshiNS.Synth.Commun.,2004,34:1447—1453I2(0.1eq),t-BuOH,70℃,55min,90%I2(0.1eq),t-BuOH,70℃,200min,75%JournalofMolecularCatalysisA:Chemical278(2007)38–41Iodine-catalyzedcouplingof4-hydroxyprolinewithisatins:Anexpeditioussynthesisof3-pyrrolylindolin-2-ones