2-萘酚不對稱偶聯(lián)反應及不對稱直接Mannich反應研究.pdf

1、中國科學院成都有機化學研究所博士學位論文2萘酚不對稱偶聯(lián)反應及不對稱直接Mannich反應研究姓名：郭其祥申請學位級別：博士專業(yè)：有機化學指導教師：龔流柱蔣耀忠20070601AbstractVanadiumComplexesCatalyzedAsymmetricOxidativeCouplingof2一NaphtholsandChiralBronstedAcidCatalyzedThree—ComponentDirectAsymmet

2、ricMannichReactionAbstractThechiralbimetallicoxavanadiumcomplexeshavebeendesignedfortheenantioselectiveoxidativecouplingof2一naphtholsbearingvarioussubstitutentsatC6and／orC7Thechiralitytransferringfromtheaminoacidtotheaxi

3、softhebiphthylwasfoundtooccuronthebasisofUVandCDspectraThehomocouplingreactionwithoxygenastheoxidantwaspromotedinthepresenceofanoxavanadiumcomplexderivedfromLisoleucineandachiralbinphenolandaffordsbinaphtholsinnearlyquan

4、titativeyieldsand謝thKghenantioselectivitiesofupto98％eeAnoxavanadiumcomplexderivedfromLisoleucineandHs—binaphtholishighlyefficientatcatalyzingtheairoxidizedcouplingof2napththols、析tllexcellentenantioselectivitiesofupto97％e

5、e51VNMRstudyshowstheoxavanadiumcomplexeshavetwovanadiumⅣ)speciesKineticstudiesandcrosscouplingreactionhavebeencarriedoutandillustratethatbothvanadiumⅣ)speciesareinvolvedincatalysisandthecoulpingreactionundergoesviaaradic

6、alradicalmechanisminanintramolecularmannerTheapplicationofthetransformationinthepreparationofchiralligandsandconjugatedpolymersconfirmtheimportanceofthecurrentprocessintheorganicsynthesisThefirstchiralBronstedacidcatalyz

7、edantiselectivethreecomponentdirectasymmetricMannichreactionhasbeendescribedThephosphoricacids，preparedfromBINOLandHs—BINOLderivatives，havebeenevaluatedforcatalyzingthereactionofcyclohexenonewitheitherNPMP—benzaldimineor