C-H键活化,chemical review

Carboxylate-AssistedTransition-Metal-CatalyzedC-HBondFunctionalizations:MechanismandScopeLutzAckermann*,Chem.Rev.2011,111,1315–1345Newwordsandphrases：stoichiometricarenecomplexeswithrespecttodimericopticallyactiveortho-slopeentropyacetatecrystallographicprecursoragosticinteractionacidityfacilehencec.p.exceedingly化学计量的芳烃复合物关于，就…而言二聚的光学活性邻位斜率熵乙酸盐结晶的前体抓氢键相互作用酸度温和的，灵巧的因此，今后化学纯非常，及其mildambientpyrroleproceedreadilyfavorableanalogousdisplacementinsitudualdimersodiumtriflatebicarbonatecarbonatenoteworthyheteroatomhydrocarbonimido温和周围环境吡咯开始，继续进行容易地有利的类似的取代，移位在反应过程中双重的二聚体钠三氟甲磺酸碳酸氢盐碳酸盐值得注意的杂原子烃类酰亚胺Newwordsandphrases：deuteriumfacilitatepyrazoleboratepronouncedcarbazoleisotopicubiquitousberestrictedtocesiumstandoutalkalimetalpivalatediastereoseletiveendothermicexothermicformatealkyneannulation氘促进吡唑硼酸盐明显的咔唑同位素的普遍存在的局限于铯突出碱金属三甲基乙酸盐非对映选择性的吸热的放热的甲酸盐炔烃环化hydroxamicmaingrouprcedoxpredominatlyunravelelectron-withdrawingisoproypylbidentatepiralicbiarylpotassiumrevisitazoleelusiverobustnesstriazoleortho-meta-para-异羟肟酸主族氧化还原反应占据主导阐明吸电子异丙基双齿的特戊酸联芳钾再论唑难懂的稳健性三唑邻位的间位的对位的1.Introduction2.StoichiometricC-HBondMetalation2.1.IntermolecularMetalation2.2.StoichiometricCyclometalations2.3.RelatedAssistedMetalationswithMonodentateBases3.CatalyticC-HBondFunctionalizations3.1.KeyObservationswithStoichiometricAmountsofCarboxylates3.1.1.ArylHalidesasArylatingReagents3.1.2.DehydrogenativeArylations3.2.CatalyticAmountsofCarboxylates3.2.1.Palladium3.2.2.Ruthenium4.ConclusionsCONTENTS1.INTRODUCTIONKeytosuccesswasgenerallyadetailedmechanisticunderstandingoftheelementaryC-Hbondmetalationstep,whichdependingonthenatureofthemetalfragmentcanproceedviaseveraldistinctreactionpathways.3Traditionalmodes:oxidativeadditionwithelectronrichlatetransitionmetalsσ-bondmetathesiswithearlytransitionmetalselectrophilicactivationwithelectrondeficientlatetransitionmetals（C-H键的金属化有多种反应模型，以下是三种经典模型，分别是后过渡金属的氧化加成；前过渡金属σ键的复分解；缺电后过渡金属的亲电激活）1.INTRODUCTIONoxidativeadditionwithelectronrichlatetransitionmetalsσ-bondmetathesiswithearlytransitionmetalselectrophilicactivationwithelectrondeficientlatetransitionmetals1.INTRODUCTIONWithinacontinuum,detailedexperimentalandcomputationalanalysisprovidedstrongevidencefornovelC-HbondmetalationmechanismsrelyingontheassistanceofabifunctionalligandbearinganadditionalLewis-basicheteroatom,suchasthatfoundin(heteroatom-substituted)secondaryphosphineoxidesormostprominentlycarboxylates.Base-assistedmetalation（经过详细的实验和计算分析，目前有一个双官能团配体和碱参与的反应机理为普遍承认的C-H键金属化的机理）1.INTRODUCTIONThisreviewcontains:Summaryofthedevelopmentandscopeofcarboxylatesascocatalystsintransition-metal-catalyzedC-Hfunctionalizationsuntilautumn2010.Discussionofexperimentalandcomputationalstudiesonstoichiometricmetalationreactionsbeingofrelevancetothemechanismofthesecatalyticprocesses.（截止至2010年秋季的羧化物作为助催化剂的发展和使用范围的总结；化学计量金属化反应在催化过程中与机理的关系，并进行了实验与计算讨论）•Someacronyms：（本文反复出现的三个重要缩写词）•CMD:concertedmetalationdeprotonation（协同的金属化与去质子化）•IES:internalelectrophilicsubstitution（分子内亲电取代）•AMLA:ambiphilicmetalligandactivation（亲电和亲核金属配体的活化）2.STOICHIOMETRICC-HBONDMETALATION2.1.IntermolecularMetalationSEAr-typemechanismSEi-typemechanismsynchronousbondfissionandbondformationprotodemercurationofdiphenylmercurymercuration（汞化）protodemercuration（去汞化）（键分裂和形成同步进行的过渡态）（二苯基汞的去汞化）2.1.IntermolecularMetalation（SEAr-typemechanism）In1980,Robertsandco-workersperformeddetailedkineticstudiesonthemercurationofarenesbyHg(O2CCF3)2.Amongothers,largeprimarykineticisotopeeffects(KIE)ofkH/kD≈6disclosedin1967byKresgeandBrennanalreadyindicatedtheprotontransfertoberatedetermining.WhilepreviousmechanisticproposalshadfavoredaSEAr-typemanifoldwithdiscreteσ-complexes,Robertsandco-workersrationalizedtheirobservationswithtransitionstate1featuringasynchronousbondfissionandbondformationasillustratedinFigure1;aSEAr-typemechanismcouldnotcompletelyberuledout.Thekineticisotopeeffect(KIE)isthechangeintherateofachemicalreactionwhenoneoftheatomsinthereactantsissubstitutedwithoneofitsisotopes.Formally,itistheratioofrateconstantsforthereactionsinvolvingthelight(kL)andtheheavy(kH)isotopicallysubstitutedreactants:kIE=kL/kH（维基百科）KIE：动力学同位素效应Notably,thismodeofactionresembledthepreviouslyproposedmechanismforthereversereaction,thatis,theprotodemercurationofdiphenylmercury,forwhichWinsteinandTraylorhadputforwardaconcertedSEi-typemechanismin1955.Arelatedbeneficialeffectofstoichiometricamountsofpivalicacidinagold-mediatedC-Hbondactivationofelectron-deficientareneswasdisclosedbyLarrosaandco-workersin2010.2.1.IntermolecularMetalation（SEi-typemechanism）•CytolysisofDiphenylmercury2.STOICHIOMETRICC-HBONDMETALATION2.2.StoichiometricCyclometalation1960s:StoichiometriccyclometalationreactionsofarenesbearingLewis-basicdirectinggroupswererealizedwithcomplexesofvarioustransitionmetals.1970s:AdditiveNaOAccanacceleratecyclometalationreactionswithiridium,platinum,orpalladiumcomplexes.•EffectofNaOAcontheCyclopalladationofAmine2DisclosedbyShaw(1972-1975)noadditive:---NaOAc(1.0equiv):84%（醋酸钠的加入能催化铱、铂和钯复合物的环金属化反应，下图中加入醋酸钠后，产率增至84%）2.2.StoichiometricCyclometala