2-萘酚不對(duì)稱偶聯(lián)反應(yīng)及不對(duì)稱直接Mannich反應(yīng)研究.pdf

1、中國(guó)科學(xué)院成都有機(jī)化學(xué)研究所博士學(xué)位論文2萘酚不對(duì)稱偶聯(lián)反應(yīng)及不對(duì)稱直接Mannich反應(yīng)研究姓名：郭其祥申請(qǐng)學(xué)位級(jí)別：博士專業(yè)：有機(jī)化學(xué)指導(dǎo)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