文章编号:0253-9837(2012)05-0745-12国际版DOI:10.1016/S1872-2067(11)60390-2综述:745~756二氧化碳作为羧化试剂用于羧酸及其衍生物的合成张文珍*,吕小兵大连理工大学精细化工国家重点实验室,辽宁大连116024摘要:二氧化碳是储量丰富、廉价易得且可再生的C1资源,将其催化转化成高附加值精细化学品的研究已经引起了人们的广泛关注.目前,虽然二氧化碳用作初始原料的反应已经工业化的很少,但过去几十年中仍有二十多个具有实际应用前景的二氧化碳参与的新反应被发现,其中以二氧化碳作为羧化试剂合成各种羧酸及其衍生物的反应为突出代表.本文综述了过渡金属催化合成羧酸及其衍生物的二氧化碳与多种碳亲核试剂、碳氢键以及碳碳多重键化合物的反应,并总结了无过渡金属参与或有机小分子催化条件下将二氧化碳转化成羧酸及其衍生物的反应.关键词:二氧化碳;羧酸及其衍生物;羧化反应;氢羧化反应;均相催化中图分类号:O643文献标识码:A收稿日期:2012-02-20.接受日期:2012-03-23.*通讯联系人.电话:(0411)84986257;传真:(0411)84986256;电子信箱:zhangwz@dlut.edu.cn基金来源:国家自然科学基金(21172026,U1162101);国家重点基础研究发展计划(973计划,2009CB825300).本文的英文电子版(国际版)由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).SynthesisofCarboxylicAcidsandDerivativesUsingCO2asCarboxylativeReagentZHANGWenzhen*,LÜXiaobingStateKeyLaboratoryofFineChemicals,DalianUniversityofTechnology,Dalian116024,Liaoning,ChinaAbstract:Thecatalytictransformationofcarbondioxideintohighvalue-addedfinechemicalshasattractedattentionbecausethiswillmakeCO2intoanabundant,inexpensive,andrenewableC1feedstock.Morethan20reactionsinvolvingCO2asastartingmaterialhavebeende-velopedinrecentdecadesbuttheirsuccessfulindustrializationislimited.OnetypeofreactionsthatistechnologicallyviableistouseCO2asacarboxylativereagentintheproductionofawiderangeofcarboxylicacidsandderivatives.Thisreviewfocusedontransitionmetal-catalyzedreactionsforthesynthesisofvariouscarboxylicacidandderivativesfromCO2,bythecarboxylationofcarbonnucleophilesandC–HbondsandreactionsofCO2withunsaturatedorganiccompounds(especiallythosewithacarbon–carbonmultiplebond).Thisre-viewalsoincludedtransitionmetal-freeororganocatalyticreactionsforthetransformationofCO2intocarboxylicacidandderivatives.Keywords:carbondioxide;carboxylicacidsandderivative;carboxylation;hydrocarboxylation;homogeneouscatalysisReceived20February2012.Accepted23March2012.*Correspondingauthor:Tel:+86-411-84986257;Fax:+86-411-84986256;E-mail:zhangwz@dlut.edu.cnThisworkwassupportedbytheNationalNaturalScienceFoundationofChina(21172026,U1162101)andtheNationalBasicResearchProgramofChina(973Program,2009CB825300).EnglisheditionavailableonlineatElsevierScienceDirect(http://www.sciencedirect.com/science/journal/18722067).TheincreaseofCO2intheatmosphereanditsimpactontheenvironmentisanimportantissuefortheworld.ThisissuehaspromptedefforttoreduceCO2emissionsandtodevelopefficientcatalyticprocessesfortransformingthismaingreenhousegasintovaluablecompounds,whichwillmakeCO2anabundant,nontoxic,andinexpensiveC1feed-stock[1–10].Carboxylicacidsandderivativesarecommonstructuralunitsthatarefrequentlyfoundinavastarrayofnaturalproducts,andtheyarehighlyversatilestartingmaterialsforthepreparationofbiologicallyactivecompoundsandotherfinechemicals.Thetransitionmetal-catalyzedcarboxylation催化学报746Chin.J.Catal.,2012,33:745–756ofvariousnucleophilesorunsaturatedhydrocarbonsthatuseCO2asacarboxylativeagentisanattractiveroutetoproducecarboxylicacidsandderivative...