官能团转化全图解

word格式文档专业整理·word格式文档专业整理i5-7-gfedcbaedcbaihgfedcbahgfedcbahgfedcba6-4-3-1-2-ihgfedcbaC=C-C(O)-CH3CH-CHCH-CXFunctionalGroupInterconversionC=CCCC=CCCRCH2-SO2PhRCCHCCC-NH2;C-NO2C-OHC(OR)2;C(SR)2C=C-OR;C=C-SRCCCNC=N-OH,C=N-HC=SC=OC=OC-C(O)ZC=CC=OC-OHC-XC-NC-HC-NC=OC---OHC-OC(O)RC-XC-OCH2ORC-NH2C-ORC-HC-OHC=CC-HC(O)ORC-(OR)2C-OHC-ORC-CHOC-CO2HC-CNC=CC=OC-SC-XC-OHC-HC=CjC(O)XhCNjkC-HC-Br8-C-XiC-OHC-OHC(O)ZdcbaedcbafC-NH2C-HjCX-CYCCXC=OhgfiCCHRCH(CO2H)-CH3-C(O)-CH3OOOXCRR'=CHXjCOC-NH2C-CN9-C-CH3C-XaeC=Oword格式文档专业整理1-adrypyridine:fromCaH2anddistilled(anester)triflatemesylatetosylateSOOORCH2CF3SOOORCH2CH3thiocarbonatedryPyCH3CH3CH3OH(2).for3'alcohol:LiAlH4(1).for1',2'alcohol:C-HC-OH1-ihgfedcbaC-CHOC-CO2HC-CNC=CC=OC-SC-NH2C-XC-OHC-HOCSOPhSnBu3CH3CH3CH3Hn-Bu3SnHCSOPhClOCSOPhRCH2-HCH3SOOORCH2CH3SOOClRCH2OHstericOKpurificationtextbook~$30/Kgtoluenesulfonylchloride(s)methanesulfonyychloride(l)~$30/KgjC(O)XPh2SiHCl/InCl3PhPhHPhOHPhJOC,2001,66,7741.ii.Ph2SiHCl/InCl3i.p-TsCl//LiAlH4i.ClC(S)OPh//n-Bu3SnHPhPhOCl2InClSiPh2Hvia:via:auniqueLewisacidcatalyst,acceleratedeoxgyenationInCl3indiumtrichlorideii.Et3SiH/LewisacidJ.Org.Chem.2000,65,6179JOC,2000,65,6179.CHCl2rt,3hrword格式文档专业整理1-bBu3SnH:(l),easytoremovePh3SnH:(s),hardtoremoveMe3SnH:toovolatile,toxic(AIBN)NNCNCN-N2CNazobisisobutyronitrilen-BuSnHn-BuSnBrRn-BuSnBrRHRunstableinacid,formH2gas;stableinweakbaseNaBH3CN:stableatpH5-6hygroscopic,driedself,suggest:buysmallamounteachtime(Grignardreagent)H2OMg/Et2OJOC,1969,34,3923.HBrNa/NH3;Li/NH3;Na/EtOHZn;Fe;Sn;Mg(3).metalreduction(2).hydridereduction(1).freeradicalreductionJACS,1972,94,8905.C-HC-XAIBNn-Bu3SnHHBrradicalinitiatorNaBH4/InCl3/CH3CNradicalreagentn-Bu3SnH/AlBNJACS,2002,124,906.iiiiNaBH3CNiLiAlH4iiiiiNaBH4iiTHL,1969,3095.JOC,1976,41,3064.ivLiBHEt3(superhydride)n-BuSnHn-BuSnword格式文档专业整理mechanismuncertain,probablyradicalburnfilterpaperifdryRaneyNickel:Ni-Alalloy,suspensiontosylimidetosylamideJCSPerkinTransI,1973,654.(3).LiAlH4/CuCl2NaBH4/NiCl2NaBHEt3/FeCl2(orCoCl2,VCl3)(2).Li/NH3(1).RaneyNiNSO2ArSO2ArRCH2RCH2NSO2Ar-BuHRCH2NHSO2ArBuLiLiAlH4RCH2-HCH3SOOClRCH2NH2BuLi1-d1-cC-HC-SLiAlH4C-HC-NH2RCH2-HRCH2NH2Hinsberg'stestradicalmechanismweakerC-NbondChemistry:R-SHR-S-RR2SOR2SO2R-SS-Rremove:Hg+;Ni(1).(2).Ar-HNaNO2HClH3PO2Ar-NH2RCH2NH2RCH2NMe3R=CH2R-CH3(4).X-RCH2NMe3OH-Ag2OJOC,1985,50,427.p-TsClNaHNaHp-TsClNH2Clvia:NNH2SO2ArArNaHNNHArNNArAr-H-ArSO2H(3).Ar-NH2Ar-Hp-TsClJOC,2001,66,8293.ArSO2ClRaneyNiNHNSMeO2CCH2PhEtO2CONHNHMeO2CCH2PhEtO2Cword格式文档专业整理foracyclic,mayC=CsideproductbasicneutralacidicHHH-NNTsCH2Cl2C=OC-H1-e(1).Clemmensenreduction:Zn-Hg/HCl(2).thioketal:(3).Wolff-Kishnerreduction:(5).Tosylhydrazonereduction(Shapiroreaction):(modifiedWolff-Kishnerreduction):)(6).enolderivatives:SHSH/BF3,CH2Cl2//RaNiN2H4,OH-,heatTsNHNH2//REDlimit:for-Hcompd.HHRa(Ni)BF3,SSHHSSHHOthioketal:inerttoLAH;reactwithRaNi;smellterribleandstaylong;discardshosesthioketalmajorside-product:drawbackofthereactionNN-N2OH-HNNHNNHOH-NNH2N2H4OHHNCHCOCF3SOOOSOCF3OCCOTfH2PtO2CCHHHTf2O/N//H2/PtO2LAH,NaBH4:2groupcompeteatStanfordU.B2H6:veryflamable,fireifshootoutfromsyringeOOBHbestsuitableforarylketone(ArCOR);notgoodforconjugateketonepreparation:HgCl2intoZnREDchoice:MeLi;NaBH3CN(good)PtO2+H2=PtOHOC6H13similar:Sn/HCl(4).Pd-C/HCO2NH4:mild,efficientPhPhOPhPhSynthesis,2001,16,2370.HCO2NH4Pd-C(7).Et3SiH/CF3COOHPhONO2PhNO2JOC,1973,38,2675.CF3COOHEt3SiHword格式文档专业整理HOOHHHPtO2H2HOOH$50/25gJOC,1993,58,4979.syn-additionprepareisotopeCH3CO2DHDC=CC-C-H1-f(1).H2/cat(2).HN=NH(diimide)(3).B2H6//RCO2H,heatWilkinson'scatalyst:regioselective,preferisolateddoublebondsolubleinorgsolvent,9Phgroupstereoselcetive:samesideasOH(duetoHbond)catalyst:Pd-CPtO2Rh-C;Rh-Al2O3;RhCl(PPh3)3NiOORhCl(PPh3)3N2H2:unstable;generatedinsitufromDEAD(diethylazodicarboxylate)orfrom:N2H4+H2O2;N2H4+Cu(II)+O2;NH2OH+NH2OSO3via:HBRRNNCO2EtEtO2CNNCO2HHO2COH--2CO2NNOOHOOHNNHH-N2CCRRRRCCRRRRHHJCS,PT1,1986,546.OOCO2MeOOCO2MeRhCl(PPh3)312hrJACS,1979,101,7020.NRNRH2,PtO2TFA,60℃R=NHAc,NH2JOC,2002,67,7890.inaceticconditionbenzene(4).n-Bu2SnI/MgBr2-Et2O//H3O+OEtOH3O+OEtOMgBr2-Et2On-Bu2SnIJOC,2001,66,8690.OSnHOEtIRROOEtSnIRHRvia:notradicalmech.word格式文档专业整理pyridiniumbetainesolventNPhPhPhRRHNPhPhPhRRCO2-CO2b.p.~230Chighlytoxic,cancersuspectedagent?=HMPT:hexamethylphosphorictriamide(Me2N)3P=Otoxic?characteristcs:IR,CMRwhichis+?CCRNnotquitesame:notforH-e-CO2HCO2H(3).organicelectrochemistry-CO2(1).particularstructure:C-H1-g(1).K/Al2O3K/HMPA(2).Na/NH31-h(2).normalstructure:SOCl2//PhSeH//n-Bu3SnHCCNJOC,1980,45,3227CN:~X(pseudohalogen),formKCN,NaCNwithIAelementsHMPA:hexamethylphosphoramide(Me2N)3P=Oyesforwhitemouse,uncertainforhumanmodifiedto:NNOCCO2HC-HCOSePhRCH2RCH2HCOOHRCH2COClRCH2PhSeHn-Bu3SnHSOCl2(radicalmechanism?)otherClsources:PCl5;(COCl)2oxalylchlorideorganoseleniumchemistryOHOROword格式文档专业整理1-iCHOC-H(1).RhCl(PPh3)3(Wilkinson'scat)(2).Rh(DPPD)2+Cl-oxidativeadditionrearrangementreductiveeliminationRhPPh3PPh3CClO+RHRhPPh3PPh3CROClHRhPPh3PPh3ClHRCORCOHRhPPh3PPh3Cl-PPh3ClRhPPh3PPh3PPh3DPPD=Ph2P-CH2CH2-PPh21-jC(O)X-CH3RClORCH3H