allosteric cofacial porphyrin complexes超分子变构cofacial卟啉配合物课件

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1、SupramolecularAllostericCofacialPorphyrinComplexesChristopherG.Oliveri,NathanC.Gianneschi,SonBinhT.Nguyen,*,ChadA.Mirkin,*,CharlotteL.Stern,ZdzislawWawrzak,andMarenPinkJ.Am.Chem.Soc.2007,128,16286-16296Speaker：鍾柏源1AllostericRecognitionChadA.Mirkinet.al.Angew.Chem.Int.Ed

2、.2006,45,941–944Theallosteric-effector-mediatedshapechangeofamacrocycle.2Introduction-Porphyrin丁裕生碩士論文，國立中興大學物理研究所，93年3Chlorophy11VitaminB124Holliday,B.J.et.al.Angew.Chem.Int.Ed.2001,40,2022-2043.SupramolecularCoordinationChemistryHydrogenbondingp-pinteractionMetaltolig

3、andbindingvanderWaalsforces5TheDirectional-BondingApproachHolliday,B.J.et.al.Angew.Chem.Int.Ed.2001,40,2022-2043.6TheSymmetry-InteractionApproachDinuclearstructuresTetranuclearstructuresThesymmetry-interactionsyntheticstrategyhasgrantedresearchersaccesstoavarietyofelega

4、ntshapesandarchitectures(forexample,helicates,tetrahedra,andadamantoidstructures)throughthepredictablecoordinationchemistryofmultibranchedchelatingligandswithtransitionandmaingroupmetalcenters.Holliday,B.J.et.al.Angew.Chem.Int.Ed.2001,40,2022-2043.7TheWeak-LinkApproachA

5、criticalfeatureofthisapproachisthatthemetalsusedintheassemblyprocessareavailableforfurtherreactionswithoutdestroyingthesupramolecularstructure.Thisapproachtargetscondensedstructuresthatcontainstrategicallyplacedstrong(metal-phosphine)andweak(metal-X)bonds.Mirkin,C.A.Acc

6、.Chem.Res.2005,38,825-837.8CatalyticAcylTransferbyaCyclicPorphyrinTrimerSanders,J.K.M.et.al.J.Am.Chem.Soc.1994,116,3141-3142.Tetrahedralintermediatedoubly-boundinsidecavityoftrimer.Schematicviewofaproximity-catalyzedtransferreaction.9DesignofAllostericPorphyrin-BasedSup

7、ramoleculesClosedmacrocycleOpenmacrocyclePPh2=diphenylphosphineMES=1,3,5-trimethylbenzene10(i)1-bromo-2-chloroethane,K2CO3,Acetone,Reflux(ii)1,3-propanedithiol,Y(OTf)3(5mol%),CH3CN(iii)KPPh2,THF(iv)S8,THF(v)NaNO2,AcCl/H2O,CH2Cl2,0°C→rt75%86%97%SynthesisofEther-BasedLiga

8、nd7andMacrocycles8aand8bY(OTf)311(vi)5-mesityldipyrromethane,BF3‧OEt2,DDQ,NEt3,CHCl3,4ÅMolecularSieves(vii)Zn(