C-H键活化,chemicalreview论述.pptxVIP

Carboxylate-Assisted Transition-Metal- Catalyzed C-H Bond Functionalizations: Mechanism and Scope;New words and phrases：;New words and phrases：;1. Introduction 2. Stoichiometric C-H Bond Metalation 2.1. Intermolecular Metalation 2.2. Stoichiometric Cyclometalations 2.3. Related Assisted Metalations with Monodentate Bases 3. Catalytic C-H Bond Functionalizations 3.1. Key Observations with Stoichiometric Amounts of Carboxylates 3.1.1. Aryl Halides as Arylating Reagents 3.1.2. Dehydrogenative Arylations 3.2. Catalytic Amounts of Carboxylates 3.2.1. Palladium 3.2.2. Ruthenium 4. Conclusions;1.INTRODUCTION;1.INTRODUCTION;1.INTRODUCTION;1.INTRODUCTION;2.STOICHIOMETRIC C-H BOND METALATION;2.1. Intermolecular Metalation（SEAr-type mechanism）;Notably, this mode of action resembled the previously proposed mechanism for the reverse reaction, that is, the protodemercuration of diphenylmercury, for which Winstein and Traylor had put forward a concerted SEi-type mechanism in 1955 . A related beneficial effect of stoichiometric amounts of pivalic acid in a gold-mediated C-H bond activation of electron-deficient arenes was disclosed by Larrosa and co-workers in 2010. ;2.STOICHIOMETRIC C-H BOND METALATION;2.2. Stoichiometric Cyclometalation;Proposed transition state 6 for ortho-palladation of DMBA-H.;This agostic interaction enhances the acidity of the ortho-proton, which enables a subsequent facile intramolecular deprotonation by the coordinated acetate. （抓氢键增强了邻位氢的酸性，随后发生了乙酸盐的辅助下的温和的分子内去 质子化过程） ;2.2. Stoichiometric Cyclometalation;2.2. Stoichiometric Cyclometalation;2.2. Stoichiometric Cyclometalation;2.2. Stoichiometric Cyclometalation;2.STOICHIOMETRIC C-H BOND METALATION;Proposed Mode of Action for C-H Bond Metalation with an Iridium(III)-Hydroxide Complex ;2.3. Related Assisted Metalations with Monodentate Bases;3.CATALYTIC C-H BOND FUNCTIONALIZATIONS;The elegant synthes