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1、2001年第21卷有机化学Vol.21,2001第1期,75~81ChineseJournalofOrganicChemistryNo.1,75~81#学术动态#以N-杂环卡宾为配体的金属络合物催化有机合成的反应X李林涛麻生明(中国科学院上海有机化学研究所,金属有机化学开放实验室上海200032)摘要综述了近几年来以N-杂环卡宾为配体的金属络合物催化有机合成的反应。关键词N-杂环,卡宾,金属络合物,催化,反应OrganicTransformationsCatalyzedbyN-HeterocyclicCarbene-MetalComplexes*
2、LILin-Tao,MASheng-Ming(LaboratoryofOrganometallicChemistry,ShanghaiInstituteofOrganicChemistry,ChineseAcademyofSciences,200032Shanghai)AbstractReactionscatalyzedbyN-heterocycliccarbene-metalcomplexes,suchasolefinmetathesis,couplingre-action,hydrosilylationreaction,etc.wererev
3、iewed.Ruthenium(II)complexesbearingoneortwoimidazolin-2-ylideneligandsarehighlyactivecatalystsforalltypesofringclosingmetathesisreactions.Importantly,theyevenallowtheformationoftetrasubstitutedalkenesthatwerenotpre-viouslyachievedbyruthenium-phosphinemetathesiscatalysts.Inadd
4、ition,functionalizedolefinsweresynthesizedbyin-termolecularcross-metathesisandring-closingmetathesis.Palladium(0)complexesofimidazolin-2-ylidenes(19)couldnotcatalyzethecouplingofp-chlorotolueneandphe-nylboronicacid.However,asystemconsistsofaPd(0)precursoranddihydroimidazoline
5、carbeneligand,whichisgen-eratedinsitu,showedhighactivityforSuzukicross-couplingreactionofarylchlorideswitharylboronicacids,Kumadacross-couplingreactionofarylchlorideswitharylGrignardreagentsandaminationofarylchlorides.Complexesofthe(NHC)Pd(PR3)I2-typewithbulkyN-heterocyclicca
6、rbenes(NHC)areefficientcatalystsfortheSuzukiandStillecross-couplingreactions,etc.Imidazolidin-2-ylidenederivativesofrhodium(I)andruthenium(II)catalyzethecarbon-carboncouplingofterminalalkynes,thecyclopropanationreactionsofdiazoalkanederivativeswithstyrene,hydrosilylationofalk
7、enes,alkynes,ke-tonesandhydrogenationofolefins.Keywordsheterocycles,carbenes,metalcomplex,catalysis,reaction[1]自从1964年Fischer等人将卡宾引入到无机以N-杂环卡宾为配体的金属催化反应逐渐活跃起和金属有机化学中,金属卡宾在有机合成(作为试剂来。[2]或催化剂)和大分子化学中得到了广泛的应用。金属卡宾络合物1发现不久,1968年;fele和Wan-1烯烃的复分解反应[3]zlick等人发现了N-杂环卡宾的金属络合物2和烯烃的复分解
8、反应作为形成CC键的一个重[4]3。但它们仅局限于金属配合物的研究。自从[7]要工具,已广泛地应用于有机合成中。烯烃复分1991年Ard