卟啉化合物的合成

*,,(南京理工大学化工学院,江苏南京210094):,,,,,:,:;;ResearchonSynthesisofPorphyrins*TANGYing,HUBing-cheng,LIUZu-liang(DepartmentofChemistry,NanjingUniversityofScienceandTechnology,JiangsuNanjing210094,China)Abstract:Porphyrinswerewidelydistributedinnatureandplayedanimportantroleintheactivitiesoflife.Porphyrinshadbrightprospectsinvariousapplicationsowingtotheiruniquestructureandbiologicalactivity.Thesynthesisofporphyrinswasmainlyintroduced.Themethodologyforpreparationofporphyrinswasdividedintofullandsemi-synthesis,accordingtodifferentreactants.Thetwokindsofsynthesismethodsofporphyrinsweredescribedindetai.lKeywords:porphyrins;totalsynthesis;semi-synthesis*:(BK2009386);(XKF09008):(1982-),,,E-mai:[e-mail]:(1969-),,,E-mai:[e-mail],NH[1]22,18,,,P-450,[2-3][4-6],,1Fig.1NamingofnaturalcyclictetrapyrrolesIUPAC,A,B,C,D,1,,2,3,7,8,12,13,17,18;5,10,15,20(meso-)[7],,,,,1,,,,[8],2()2,5()3,4[9],,2:(1)2+2,A-BD-C(2+2)A-DB-C(2+2)(),[9],Battersby[10]2+2,A-BD-C,,A-B7520103810D-C,2Woodward[11]e62+2(3Woodward)2Battersby2+2Fig.2SimplifieddiagramofBattersbysnorth2+2synthesis3Woodward2+2Fig.3SimplifieddiagramofWoodwardseastandwest2+2synthesis(2)Johnson3+1,B-C-D(),A(A-B-CD)Montforts3+1,B-C-D(),[9,12-13],4Montforts3+1Fig.4SimplifiediagramofMontforts3+1synthesis(3),,Clezy1-9-b-,5[14]5Fig.5LineartetrapyrrolecyclizatetoPorphyrin2,,,[15-17],2.1Vilsmeier[18]Ogoshi-Vilsmeier,5-,31%28%5,15-[19],66-Fig.6Formylationreactionof-octaethylporphyrin7620103810,Senge5,15-,[20](DDQ),5,10-[21]Smith5--OEPZn()5--15-OEPH2(OEP=2,3,7,8,12,13,17,18-octaethylporphyrin)CH3MgBr5-OEPH2,,5--15-OEPH2(11%)5--OEPH2(42%),,7[22-23]75-OEPH2Fig.7Theconversionreactionof5-formylOEPH2,TherienyN-5,15-,10,20--5,15-[22]OsukaAgPF65,15-,[24],,YeungWittig,meso[22,25]2.2,Ponomarev,60%[26][7]-IX-,0,-IX-,3--IX-8--IX-3,8--IX-,88Fig.8Porphyrin-acetylationDolphin[27]N-(NCS),2,3,7,8,12,13,17,18-Ni-TPPFranckN-(NBS)meso-(2,4,6-)[22,28](9),(3,5-)-9(meso-(2,4,6-)--)Fig.9-halogenatedporphyrins(meso-Tetra(Synthesisof2,4,6-Trimethyl-phenyl)--8bromo-porphyrin)[29],,2-NO2-5,10,15,20-2-NO2-5,10,15,20-(4-)2-NO2-5,10,15,20-(4-)10102-NO2-5,10,15,20-Fig.10Synthesisof2-NO2-5,10,15,20-4ofAreneMetalporphyrins-IX-,3-(Phenylsulfonyl)-ethylpropiolate-IX-CH2Cl220h[7,30],,1111-IX-Fig.11DieneadditionoftheofProtoporphyrin-IX-dimethyl7720103810,,,PdTherien3--TPP3-TPP[31]3,,,,,,,meso--,[1]SmithKM,FalkJE.PorphyrinsandMetalloporphyrins[M].Amsterdam,Elsevier,1975(1):2-10.[2]GolubchikovOA,BerezinBD.AppliedaspectsofthechemistryofthePorphyrins[J].RussChemRev.,1986,55(8):768.[3]Dolphin.D.ThePorphyrins[M].NewYork:AcadPress,1978(1):7.[4].[J].,1982(4):228-230.[5],,.[J].,1988(1):1-7.[6],.[J].,2004(4):23-27.[7],,.[D].,2008:2-13.[8]SharghiH,NejadAH.Phosphoruspentachloride(PCl5)mediatedsynthesisoftetraarylporphyrins.HelvChim.Acta,2003,86(2):408-414.[9],,.[J].,2004,24(3):270-280.[10]BattersbyAR,TurnerSPD,BlockMH,ShengZ-C,ZimmermanSC.SyntheticstudiesrelevanttobiosyntheticresearchonvitaminB12.Part8.Synthesisof()-Faktor-Ioctamethylester.J.Chem.Soc,PerkinTrans.,1988(1):1577-1586.[11]WoodwardRB,AyerWA,BeatonJM.,BickelhauptF,BonnettR,BuchschacherP,ClossGL,DutlerH,HannahJ,HauckFP,ItoS,LangemannA,LeGoffE,LeimgruberW,LwowskiW,SauerJ,ValentaZ,VolzH.Thetotalsynthesisofchlorophyl.lJ.Am.Chem.Soc,1960,82(14):3800-3802.[12]MontfortsFP,SchwartzUM.EingezielterAufbaudesChlorinsystems.LiebigsAnn.Chem.,1985:1228-1253.[13].[D].,2004.[14]ClezyPS,MirzaAH,RaviBN,VanThucL.Thechemistryofpyrroliccompounds.LIV.Thechemistryofrhodins,verdinsandrelatedcompounds.Aust.J.Chem.,1984,37(1):143-154.[15]JohansenJE,PiermattieV,AngstC,eta.lReciprocalconversionofthechromopheresystemofporphyrinogenand2,3,7,8,12,13-hexadehydroporphyrin.AngewChem,1981,93(3):273-275.[16]WaditschatkaR,EschenmoserA.Chemistryofpyrrophins:stereoselectivityduringporphyrinogen-pyrrocerphintautomerism.AngewChem,1983,95(8):639-640.[17]FaesslerA,PfaltzA,MuellerPM,eta.lPreparationandpropertiesofsomehydrocorphinoidnickel(II)complexes.HelvChimActa,1982,65:812-816.[18]ArnoldDP,JohnsonAW,MahendramMJ.Somereactionsofmeso-formyloctaethylporhyrin.J.Chem.Soc,PerkinTrans.1978,1:366-370.[19]WatanabeE,NishimuraS,OgoshiH,YoshidaZ.Orientationofelectrophilicmeso-substitutioninmetallooctaethylporphyrins.Tetrahedron,1975,31(11):1385-1390.[20]FengXM,SengeMO.One-potSynthesisofFunctionalizedAsymmetric5,10,15,20-SubstitutedPorphyrinsfrom5,15-Diaryl-or-Dialkyl-porphyrins.Tetrahedron,2000,56(4):587-590.[21]HatscherS,SengeMO.Syntheticaccessto5,10-disubstitutedporphyrinsTetrahedronLett.,2003,44(1):157-160.[22],.meso-[D].,2005:4-8.[23]JiangX,NurcoDJ,SmithKM.J.Chem.Directmeso-alkylationofmeso-formylporphyrinsusingGrignardreagents.Soc.Chem.Commun.,1996:1759-1760.[24]NakanoA,ShimidzuH,OsukaA.Facileregioselectivemeso-iodinationofporphyrinsTetrahedronLett.,1998,39(51):9489-9492.[25]YeungM,NgACH,DrewMGB,VorpagelE,eta.lFacileSynthesisandNonlinearOpticalPropertiesofPush-Pull5,15-Diphenylporphyrins.J.Org.Chem,1998,63(21):7143-7150.[26]PonomarevGV,MaravinGB.Porphyrins.14.Synthesisandpropertiesof1-substitutedderi