1、word格式文檔專業(yè)整理word格式文檔FunctionalGroupInterconversionC-H1-abcdefghi飛C-OHC-XC-NH2C-SC=OC=CC-CNC-CO2HC-CHOC-OR-1|C-OH一C-NC=O2-aC(O)XC-OHC-(OR)2C(O)ORC-HC=CC-CN3-aC-H4-aC-HbC-ORbC-NcC-XcC-XdC-NH2dC-OHeC-OCH2ORfeC=OTC-OC(O)RfC=CgC-OHgC-C(O)ZhC=OiC=OhC=NC=C5-abcdefghikC=OC=SC=N-OH,C=N-HC三CCNC=C-OR;C=C-SRC(O

2、R)2;C(SR)2C-OHC-NH2;C-NO2C-BrC-HCC-8clC-X-C-CH36-aRC三CH7-aCH-CX8-aC-OH9-aC-XbRCH2-S02PhbCH-CHbC-NH2cC三CcCX-CYcC=OdC=CXdc-cdC(O)ZeRCH(CO2H)-CH3eC-Hehi-C(O)-CH3專業(yè)整理-C(O)-CH3C=OCCC三CHC=CC-OHword格式文檔C-H1-aC-0HeC=OiC-CHObC-XfC=CjC(O)XcC-NH2gC-CNdC-ShC-CQHJ.Org.Chem.2000,65,-aC-OH-C-H(1) .for1,2alcohol:i.

3、 “sCl/LiAlHOc一RCHOHdryPyLiAlH4RCH-HRCH2OSCH3RCH-O-S-CH3IIOOIIRCH2OSCBIftOtosylatemesylatetriflatetoluenesulfonylchlorides$30/Kgmethanesulfonyychlorid$)30/Kgpurificationtextbookdrypyridine:fromC2aHnddistilledii. PhSiHCl/InClOHPhSiHCl/InClCHC2rt,3hrPhPhYHJOC2001667741.indiumtrichlorideInC3auniqueLewis

4、acidcatalyst,acceleratedeoxgyenation(2) .for3alcohol:i. ClC(S)OPhn/BuSnHCH3CH3CH340HCl-C-0Phn-Bu3SnHCHHACH3CH3ii. EfeSiH/LewisacidJOC2000656179.SnBuSS.-OCO-PhOCOPh.一via:,thiocarbonate(anester)stericOK專業(yè)整理word格式文檔1-bC-X-AC-Hin-BuSnH/AlBN(1).freeradicalreductioniiNaBH/InC3/CH3CNn-Bi3SnHAIBNBifeSnH:(l)

5、,easytoremovePh3SnH:(s),hardtoremoveMeaSnH:toovolatile,toxicJACS,2002124,906.radicalreagentiLiA1H41JACS1972948905.hygroscopic,driedself,suggest:buysmallamounteachtimeunstableinacid,formgas;stableinweakbase(2) .hydridereductionNaBhl(JOC11969343923;iTHL,19693095.JiiiNaBHCNNaBHCN:stableatpH5-6ivLiBHE3(

6、superhydride)jOC,1976413064.BrMg/E2OH2O(Grignardreagent)(3) .metalreductionNa/NHLi/NH3；Na/EtOH1iiZn;Fe;Sn;Mg專業(yè)整理word格式文檔1-cc-nh2*C-HJp-TsCl(1).RCH2NH2BuLiLiAlH4RCH2-HArSO2ClRCH2NH2HinsbergstestRCH2NH-SO2ArBuLtosylamide-BuH(2).Ar-NH2p-TsClNaHNH2ClNaHAr-HClp-TsClCH(3).Ar-NH2NaNO2H3PO2Ar-HHClSO2Arvia:A

7、r-NNaH.NH22-ArSO2H(4).RCH2NH2X-RCH2NMe3XAg2ORCH2NMe3OH-R=CH2R-CH3GRCH2N-SO2ArSO2ArLiAlH4rch2nRCH2-HSO?ArtosylimideweakerC-NbondArN=NH.ArN=N-Ar-HJOC,2001,66,8293.1-dC-S-C-H(1).RaneyNi(2).Li/NH3(3).LiAlH4/CuCl2NaBH4/NiCl2radicalmechanismRaneyNickel:Ni-Alalloy,suspensionburnfilterpaperifdrymechanismunc

8、ertain,probablyradicalJCSPerkinTrans1,1973,654.NaBHEt3/FeCl2(orCoCl2,VCl3)專業(yè)整理Chemistry:R-SHR-S-RR2SOR2SO2R-SS-Rremove:Hg+;Niword格式文檔1-eC=OC-Hbestsuitableforarylketone(ArCOR);notgoodforconjugateJejOnepreparation:HgCtbZn(1).Clemmensenreduction:Zn-Hg/HQcidicsimilarSn/HClOHOCoH13(2).thioketal:lSH匚sHB旦C

9、HC2RaNineutral(3).Wolff-Kishnerreduction1HU0Hheat(basic(4).Pd-C/H2NBUmild,efficient.OPd-CPhPhPhPhHCONH4Synthes200,1162370(5).Tosylhydrazonereduction(Shapiroreaction):(modifiedWolff-KishnerreducTsn)HNH/RED(6).enolderivativesfO/(7).ESiH/C3COOHhi?/PtOlimit:for-Hcompd.JOC197338,2675.專業(yè)整理B凡CHCbHSHHS、Ra(N

10、i)SHthioketalthioketal:inerttoLAH;reactwithRaNi;smellterribleandstaylong;discardshosesOHOHmajorside-product:drawbackofthereactonON2H4，NNTsH-HHforacyclic,mayC=CsideproductREDchoice:MeLi;MCBH(good)LAH,NaBJH2groupcompeteatStanfordU.B2H6veryflamable,fireifshootoutfromsyringeHOiiiC-CooIIiiCgSO_SCqRC-O-TB

11、DMSRC-O-TBSii.abbrev.:TBDMS=tert-butyl-dimethylsilyl=TBS=aromaticsubstitutionreactionusuallycontainNO2,Fasleavinggroup0cH3HClOCH3AlCl3，為OCH3OCH3OLiAlH4OHword格式文檔2-cORCOR(1).hv/HSiCl3.HCl/tBu-OO-tBuRC-ORSiCl3radicalmechanism:t-BuORaNiwithC=S(3).Lawessonreagent/RaNi(4).BF3/NaBH4limitfor:lactoneJOC,197

12、4,39,2470.)2(RC-HRC-OR(1).I2/Pb(OAc)4/hvAngewChemIntEng.,1964,8,525.limit:for56ringneighboringOHgroupOHI2/Pb(OAc)4(2).OrganoelectroChemistry:e-/Pt,R4NOTS.NCS/MeOHJOC,2002,67,4498.一limit:forallylicalcohol專業(yè)整理PhN,O=：NHHHNH2NCSHOhvR4NOTsPhPh(79%)白e/PtORMgBrH0cH3NO：INHseemech-13OIHOMeOHNH2word格式文檔2-eC-C

13、-ORCOCC=C-ORHg(OCCF3)2OEtOHHg_OrCCF3.NaBH4OEtperacid:CF3CO3Hgoodresult2-e.ic=CC-C-ORi.Hg(OCOCF3)2,ROH/NaBH4ii.HCHOHCHO(aq)H2OHCHOCO3Hco2hCO3HperoxybenzoicacidPrinsRxnvia:(Synthesis,1980,871.OHOHOHCO3HMCPBA(m-chloroperoxybenzoicacid)stablesolid,85%(containMCBA)forsafetyOlimitforallylalcohol,2-e.2CCCC

14、highe.e.mCPBAi.peracidii.viahalohydrin:HOBr,H2O/K2CO3HOBrH2O2-e.3iii.Sharplessasymmetricepoxidation:t-BuOOH,Ti(OiPr)4/(+)-diethyltartrateiv. t-BuOOH,Mo(CO)6HOv. KHSO5potassiumhydrogenpreoxideconvenient,inexpensive,powerful.vi.H2O2,t-BuOH,MnSO4/NaHCO3,pH8new,cheap,simple,greenchemistryC=C-C=C-ORBr2/R

15、OH八OHHO2cOO2-fC*C=N-C-C-OREtC=NEtOHEt-ROH/HClHCl專業(yè)整理Sharplesso-oOracemicproductsOracemicproductsBrOHtrans-diaxialattack!HOBrgeneration:NBS+H2O+DMSOstereoselectiveHOCO2EtH1OHHO七HCO2Et(+)-diethyltartratechiralsourceJOC,1980,45,4758.HO2CJOC,1982,47,2670.JOC,2001,66,521.OJACS,2001,123,2933.OOvia:HOEtC-O

16、EtOEtHeterocyclicChem,1990,27,583.JACS,1942,64,1825.conversionOOHOAcOSO2MeOHOSO2MeHOAcOAcword格式文檔3.aC-HC-NH2C-ORC-XeC-OCH2ORC-OC(O)RC-OHC=OCOC=C3-aC-H3-a.i3-a.2C-OHNO20OHPhI(OAc)-O2-Mn(TPP)JACS,1983,105,2920.H2OJACS,1983,105,3515.indirect(3).X2/hv/OH-OHHOHforallylH:OH(1).PhI(OAc)-O2-Mn(TPP)(2).organ

17、icelectrochemistrySe.HO；：OHNH2OSeHSe-HO-OJACS,1972,94,7154.OMe3SiClRH2OOHSe(OH)23-a.3O,OHJOC,1975,40,3427.(1)MesSiCI/MPCBA/H3O+Ph1.MeaSiCIOH2.MCPBAPh(2).O2,LDA,(EtO)3PJACS,1975,97,6909.RO(EtO)3PCO2RO2,LDA,ROOHCO2R專業(yè)整理PhH3OPhvia:OSiMe3PhOSiMe3MCPBAPhOSiMe3OHIOHROOrROOPOEtOEtOOHPhword格式文檔L3-bC-ORC-OHa

18、pplication:deprotectingi. TMSIii. BF3-Et2O/R-SH(orHS-CHCH2-SH)Me3Si-ISiMe3I-RCH2-O-CH3RCH2O,RCH2-O-SiMe3RCH2-OH-ICH3-CH3I(1).Me:RC-OCH3iii. BBr3/CH2clz0-10Civ. AlCl3/RSHTHL,2001,42,9207.v.HCl-/heatvi./LiI,heatBF3RCH2-O-CH3-RCH2ORSHrch2-ohCH3-RSCH3MeO-CO2MeA1cJH0CO2Me(2).PhCH2-RC-OCH2Ph=RC-OBZl=RC-OB

19、ni.ii.H2/Pd-COClCN,ohClCN(3).allyl:RC-OCH2CH=CH2RhCl(PPh)3,H3O+O-CH2O-CH2OCH30.t-Bu:RC-OtBu(5).trityl:JOC,1973,38,3224.i. TFA(CF3cO2H)needstrongeracidii. HBr/HOAciii.TMS-IRC-OCPh=RC-OTrtriphenylmethyl(6).silyl:RC-OSiR3-SiMe3-SiBuMe2-SiBuPh2專業(yè)整理HOCH3heatH2/Pd-C-CH3ClOH-tolueneOCH3OHH3O+-EtCHOOHHOH-Me

20、3c+OCOCF3,OlCF3CO2HCH3(CH2)ii-SHodorlessOHRhCl(Pfh3)i. HOAc:weakacid:goodleavinggroupii. H2/Pd-C:reserve,toostrong,mightaffectothergroupH0cpmHOAc-PhsC-word格式文檔3-c3-d3-eC-X-C-OHnotpracticallyuseful:R-OHcheaperthanR-X(1),OH-(2) .KO2/DMSOJOC,1975,40,1678.THL,1975,3183.(3) .Ag2O/H2OC-NH2-C-OH(1).HNO2/H3

21、O+R-OC(O)RR-OH(1).Symmetry:ketal:useH3O+acetal:useHaO+(2).unsymetry:RO-MOMi,H3O+;ii.HCl/MeOH;RO-MEMRO-MTMRO-THP(2),Na2Fe(CN)5(NO)/K2CO3/H2ORO2C-(CH2)3CHRRO2C-(CH2)3CHR-K2CO3/H2OOMeOMeHaO+CH3OCH2CIJOC,1984,49,3912.RO-CH2OCH3RO-CH2SCH3_H3OCHaSCH2Cliii.BBrMe2i,H3O+;ii.ZnBr2/CH2cl2;iii.BBrMe2HgCl2/CH3CN

22、(aq.)p-TsOH/MeOHactually,acetalexchangeratherthanhydrolysis專業(yè)整理JOC,1986,51,3913.RO-HH3O+RO-CH2OCH2CH2OCH3CH3OCH2CH2OCH2ClROH3O+p-TSOHorCSARO-HRO-HRO-MOMhighlytoxic,worldtop10killer,discardRO-HnottoxicnotdangerousSO3HCHp-TSOH(p-toluenesulfonicacid)THP:tetrahydropyranSO3HOCSA(camphorsulfonicacid)word格

23、式文檔3-fOIIRCORROHcommonesters:formate=HCORKHCC3(orK2CO3orNH-)/MeOH(1),base:KHCO(orK2CO3,NH3)/MeOH;(2).acid:H3O+trifluoroacetate=C3CO2RKHCC3(orK2CO3orNH-)/MeOHNaOH(1%,or0.5N)acetate=CHCO及=ROAcKHCO(orK2CO3,orNH-)/MeOHbenzoate=PhC2R=ROBzNaOH(1%)/MeOHpivalate=tBu-CO2R=ROPvNaOH(0.5N)/EtOH3-gelectron:Na/NH

24、3(3).RED:hydride:iLiAlH4ii.NaAlH2(OCH2CH2OCH3)AGIEE,200241,3028.CH3O2CCO2cH3NaAlH2(OCH2CH2OCH3)2CeHe,r.t.HOOHC-OHCOHMitsunobuinversionSynthes981,1.PPh3/DEAD/RCQH/OHJOC,198752,4235.J*PhCOHPPh3/DEAD專業(yè)整理EtO2C-N-N-CO2EtROHPPh5.EtO2C-NNH-CO2EtROHPPhB*EtO2CNNHCO2EtPhCQHLIPhPhPhO*PhCOROH*R-O-Hword格式文檔31hC=

25、OcCOH(1).regioselective:LAHalmostall:ald,ketone,acie,ester,acylX,anhydrideNaBH4notforacid,ester(butLiBH4workforester)B2H6notforester,acylX,anhydride;solvent:THF,SMe2(2).stereoselective:3-ifromtop:LiAlH4;NaBH4;Na/NH3frombottom:Al(OiPr)3/iPrOHIrCl4/iPrOH/P(OMe)3-LiBH(secBu)3(3).HCHOreagent:HCHO/KOHHCH

26、O/Ca(OH)JACS,1935,511,903.il2Org.Syn,1925,4,53.C(CH2OH)4CH3-CHOHCHOCa(OH)2Synthesis,1994,1007.Meerwein-Pondorf-VerleyrxnHenbestrxnH.C.BrownJACS,1972,94,7159.c-cruCOCOHR3B,HOCH2cH20H/H2O2/NaOHJOC,1986,51,4925.R3Bc三。H2O2OH-HOCH2cH20HR3C-B=OH2OR3cOH專業(yè)整理word格式文檔3-jC-CCOH3-j.13-j.C-CCCCOH(1).H3O+(2).Hg(O

27、Ac)(3).B2H6,Hhydration:2,H2O/NaBH2O2/OH-,H2OCCOHOHH2Ooxymercuration-demercuration:b2hhydroboration:4OHOHJCS,1946,2988.trancis+tranciscis(3).H2O2/HCO(4).Na/EtOHHg(OAc)2RRCHCR(1).KMnO4/NaOH(2).OsO4RRCH-C-RJACS,1945,67,1786.Ann,1949,561,165.HgOhOAcRNaBH4RCHC_RHOHHg(OAc)2：toxic,hardtoremoveH2O2:dangerou

28、s,skinwhiten,metaldecomposeOHOH3-k專業(yè)整理OBROHword格式文檔4-aC-N4-aC-HComparenomenclatureclass:C-HC-NC-XC-QHC=QC-NnotaveryusefulreactionC=CC=NC(Q)XC-C(Q)XSQ2NH2Ph-IQAcQAc(1).nitreneinsertionprocess:Phl(QAc)2/Fe(TPP)Cl(2).PhI=NTsJQC,2000,65,7858.(3).nitrogencationradical(viaHofmann-Loeffler-Freytag)AcQHCQQH

29、H1.SQ2ClAcQTsQ,CQQHHQAcR3C-NH2primarysecondarytertiaryR_C_NH2R_C_NHRR_C-NR2RC_QHR2C_QHR3C-QHFe(TPP)ClNHTsPhl_.NTsRucatNCSQSN二l_PhQQSNHQNH(insertion)TPP=S_QQJACS,1959,81,5209.NHMe2NNC-QNHCHQH2QMeQHNHCHQTsQNHCHClClNCSHHDMFh、.HMe?NMe2NNC-QHNCH3HQCCH3N-CH32.NaN3QNH2H，CQH2SQ4hMe2NMe2NHCl-NCH3ClN-CH3H專業(yè)整理

30、HQAcNHCHQ1.LAH2.H2/PtCQN-CH3N-CHK2CQ3TsClN；-CH3word格式文檔5.H2/Pt(S)-Csulfidedplatiumnotaffect:aromaticrings,ketones,halides,nitriles,amide,eastersJACS,1965,87,2767.2.organicelectrochemistryJOC,1999,64,2301.iiRC-N3RC-NH21.NaBH4;2.Al(Hg)iiiRC-N-MeRC-NCPhRC-NCPh3ORC-NH2H2O2/Ac2O,heat/HaO+RC-NH2H2/Pd-CRC-

31、NH21.HOAc;2.H2/Pd-CRC-NC-OtBu-RC-NH2O1.TFA;2.HClRC-NC-OPhRC-NH2H2/Pd-C“OPhNH2(CH3)3Coconc.CNBOCONHONCOtBuTFANO2BOC-OFFNH2BOC-ON58632-95-4:2-(t-butoxycarbonyloxyimino)-2-phenylacetonitrileTHL,1975,4393.$300/100gpXx.NH2BOC-ONt-XYo2EtaNH-BOCL-CO2EtEg-NiOCH3NH2DMFrt.15hrOCH3Eg-Ni:electrogeneratednickelH

32、,+口HRCNN-NHapplication:，NH2R-CO2HPhPhRHBF4-PhRCH以NH2NaN3CO2Et-TPP(Sn2)N2CO2EtR.N31. reductionA2. hydrolysisCO2HRNH2HNH2OClC-O-CH2PhH。NCOCPh”/團ONHCOHo-CO專業(yè)整理L-:-aminoacidD-：-aminoacidOHON-N-oxide-HCHONH2OCH3NHH2/Pd-CNCH31.H2O22.Ac2O3.H2ONCH3NCH3Ac2。NHNHCH2PhNCH2word格式文檔4b.3RCN-ZRC-NR一aboutHC(OEtethyl

33、orthoformate($25/1L),mayfunctionasdehydratingagentRC-NC1.HC(OEt/NaBH2.RCO/NaBHNiRC-NH2C一R-C-Nx、C1.HCHO/HCOJACS1933554579.2.HCHO/2HPd-CCQEtHHOHHCQEt原甲酸三乙酯Ochcoch.OHC(OE3)becomesH2EOOEtold:FeClMgSOinSoxhletextract,reflux40hr0EtnewpTsOH/HC(OEtEtOH,reflux5hrNH2CQEtCOOHNH2HC(OEt)NaBHHCHOhcohrNMe：ICQEt-+i

34、iRCNN三N1.RBQl/baseHCOOHR-C-N-R2.NaBHCoC6H2O專業(yè)整理mildconditionSynthesi1s979537.highyieldnotaffect:NOC=C,CN,COOR,COOHword格式文檔4-cC-XC-N1.NH33.O2.Gabriel:NKN2H44.5.PhCH2BrPhCH2NH2+(PhCH2)2NH+(PhCH2)3NPhCH2BrONOOBr-H2PhNCH2Ph4-dnotgood,usuallycontainpolyalkylationproductsO2OPhCH2NHurotropine(NHNHNHNHPhCH2

35、NH2Gabrielaminesynthesis2N2HDelepineOPhCH2Brcommercialavailable,tetramerofMeNaN3/REDUnpolungOCH3OCHHSPhOCHOCH3JOC,1988,53,NHMeC-Nnh2N2H4i.Mg/NH2Clii.Mg/PhSCHCH2Ph2。methenamine(六甲烯胺)hexamethylenetetramine(環(huán)六亞甲基四胺OHTSClSPh-NMgNH2ClRBrRMgBr2RNHOMe.LAH,NaBHi.H2/catiiZn/HCl;Al(Hg)2-N3/KOHOMeMeMeMgBrPhSN-N-N6.CH3NH2(aq)/EtOH/HCl/EtC-OHinfact:C-OHC-OTsC