22582.氮雜環(huán)卡賓與金屬配合物共催化烯丙基親核取代反應(yīng)研究

1、論文題目：氮雜環(huán)卡賓與金屬配合物共催化烯丙基親核取代反應(yīng)研究專業(yè)：應(yīng)用化學(xué)碩士生：孫哲（簽字）指導(dǎo)老師：李侃社何金梅（簽字）摘要兩種或者兩種以上催化劑參與的共催化體系，因具有高效、經(jīng)濟(jì)、綠色、操作簡單等優(yōu)點(diǎn)而引起了化學(xué)家的極大興趣，在新藥設(shè)計(jì)與合成、天然產(chǎn)物合成和組合化學(xué)中都有廣泛的應(yīng)用。共催化體系中金屬有機(jī)共催化體系由于結(jié)合了金屬催化劑和有機(jī)催化劑兩者的優(yōu)點(diǎn)已成為有機(jī)合成領(lǐng)域的研究熱點(diǎn)。本文利用共催化策略，以氮雜環(huán)卡賓和金屬NiPd為

2、共催化劑，研究了一鍋煮的串聯(lián)安息香縮合反應(yīng)和烯丙基烷基化反應(yīng)，制備出了一系列具有多官能團(tuán)的α羰基高烯丙醇化合物，并分別對它們進(jìn)行了結(jié)構(gòu)表征。（1）以各類醛和烯丙基酯為原料，利用氮雜環(huán)卡賓和金屬配合物（無水NiCl2PdCl2）為共催化劑，通過串聯(lián)的安息香縮合和烯丙基親核取代反應(yīng)得到多官能團(tuán)的α羰基高烯丙醇化合物。（2）以與安息香有類似結(jié)構(gòu)的α羥基酯型化合物和烯丙基醋酸酯為原料，利用PdCl2為催化劑，通過烯丙基親核取代反應(yīng)，制備出α酯基

3、高烯丙醇化合物，成功地實(shí)現(xiàn)了α羥基酯型化合物作為親核試劑參與的烯丙基親核取代反應(yīng)。（3）在微波輔助下，對氮雜環(huán)卡賓和金屬配合物共催化烯丙基親核取代反應(yīng)進(jìn)行進(jìn)一步的研究，與傳統(tǒng)油浴加熱的方法相比，微波技術(shù)可將氮雜環(huán)卡賓和金屬配合物共催化的串聯(lián)安息香縮合和烯丙基烷基化反應(yīng)時(shí)間由18h縮短為100min，產(chǎn)率由70%提高到85%。關(guān)鍵詞：共催化；安息香縮合；烯丙基烷基化；α羰基高烯丙醇化合物；微波輔助研究類型：應(yīng)用研究Subject:Stud

4、iesofAllylNucleophilicSubstitutionReactionCatalyzedbyNHeterocyclicCarbenesMetalComplexesSpecialty:AppliedChemistryName:SunZhe(Signature)Instruct:LiKansheHeJinmei(Signature)ABSTRACTCooperativecatalysisincludetwomecatalysi

5、shaveattractedgreatattentionofchemistsbecauseofitsmanyacteristicssuchasefficienteconomicgreensimpleoperation.Itiswidelyappliedinthedesignsynthesisofnewdrugsynthesisofnaturalproductcombinatialchemistry.Havingtheadvantages

6、ofmetalganiccatalystMetalganiccooperativecatalysisbecomesahotresearchareainganicsynthesis.InthispaperacontinuousreactioncatalyzedbyNheterocycliccarbenesNiPdcooperativecatalysiswasstudied.Thecontinuousreactionincludesbenz

7、oincondensationallylicnucleophilicsubstitution.Allylatedαhydroxycarbonylcompoundwaspreparedacterized.(1)Withthepresenceofnickel(Ⅱ)Palladium(Ⅱ)chlideasmetalcomplexcatalystNheterocycliccarbeneasganiccatalysteffectiveonepot

8、synthesisofallylatedαhydroxycarbonylcompoundwasdevelopedusingbenzaldehydecinnamylacetateasprecurssinpotassiumcarbonateTHFsolution.(2)WiththepresenceofPalladium(Ⅱ)chlideasmetalcomplexcatalystsynthesisofallylatedαhydroxyca

9、rbonylcompoundwasdevelopedusingαhydroxyestercompoundcinnamylacetateasprecurssinpotassiumcarbonateTHFsolution.Experimentalresultsshowthatαhydroxyestertypecompoundcanalsobeusedasnucleophiletoparticipateallylnucleophilicsub

10、stitutionreaction.(3)InmicrowaveassistednucleophilicsubstitutionreactioncatalyzedbyNheterocycliccarbenemetalcomplexescooperativecatalysiswasfurtherstudied.ComparedwithtraditionalmethodsofheatingoilbathMicrowaveTechnology