C-H键活化,chemical review

New words and phrases：
deuterium facilitate pyrazole borate pronounced carbazole isotopic ubiquitous be restricted to cesium stand out alkali metal pivalate diastereoseletive endothermic exothermic formate alkyne annulation 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 hydroxamic main group rcedox predominatly unravel electron-withdrawing isoproypyl bidentate piralic biaryl potassium revisit azole elusive robustness triazole orthometapara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
stoichiometric arene complexes with respect to dimeric optically active orthoslope entropy acetate crystallographic precursor agostic interaction acidity facile hence c.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 mild ambient pyrrole proceed readily favorable analogous displacement in situ dual dimer sodium triflate bicarbonate carbonate noteworthy heteroatom hydrocarbon imido 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
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
2.STOICHIOMETRIC C-H BOND METALATION
2.1. Intermolecular Metalation
SEAr-type mechanism SEi-type mechanism mercuration（汞化） protodemercuration（去汞化）
synchronous bond fission and bond formation（键分裂和形成同步进行的过渡态）
4. Conclusions
1.INTRODUCTION
Key to success was generally a detailed mechanistic understanding of the elementary C-H bond metalation step, which depending on the nature of the metal fragment can proceed via several distinct reaction pathways.
• Some acronyms：（本文反复出现的三个重要缩写词）
• CMD : concerted metalation deprotonation （协同的金属化与去质子化） • IES : internal electrophilic substitution（分子内亲电取代） • AMLA : ambiphilic metal ligand activation （亲电和亲核金属配体的活化）
Lutz Ackermann*, Chem. Rev.2011, 111, 1315–1345
Carboxylate-Assisted Transition-MetalCatalyzed C-H Bond Functionalizations: Mechanism and Scope
New words and phrases：
CONTENTS
1. Introduction 2. Stoichiometric C-H Bond Metalation
2.1. Intermolecular Metalation 2.2. Stoichiometric Cyclometalations 2.3. Related Assisted Metalations with Monodentate Bases
Base-assisted metalation
1.INTRODUCTION
This review contains:
Summary of the development and scope of carboxylates as cocatalysts in transitionmetal-catalyzed C-H functionalizations until autumn 2010. Discussion of experimental and computational studies on stoichiometric metalation reactions being of relevance to the mechanism of these catalytic processes. （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）
1.INTRODUCTION
oxidative addition with electronrich latetransition metals
σ-bond metathesis with early transition metals
electrophilic activation with electrondeficient late transition metals
（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）
3 Traditional modes:
oxidative addition with electronrich latetransition metals σ-bond metathesis with early transition metals electrophilic activation with electrondeficient late transition metals
The kinetic isotope effect (KIE) is the change in the rate of a chemical reaction when one of the atoms in the reactants is substituted with one of its isotopes. Formally, it is the ratio of rate constants for the reactions involving the light (kL) and the heavy (kH) isotopically substituted reactants:kIE=kL/kH （维基百科）
1.INTRODUCTION
Within a continuum, detailed experimental and computational analysis provided strong evidence for novel C-H bond metalation mechanisms relying on the assistance of a bifunctional ligand bearing an additional Lewis-basic heteroatom, such as that found in (heteroatom-substituted) secondary phosphine oxides or most prominently carboxylates. （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）
2.1. Intermolecular Metalation（SEi-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 goldmediated C-H bond activation of electron-deficient arenes was disclosed by Larrosa and co-workers in 2010. • Cytolysis of Diphenylmercury
protodeபைடு நூலகம்ercuration of diphenylmercury （二苯基汞的去汞化）
2.1. Intermolecular Metalation（SEAr-type mechanism）
In 1980, Roberts and co-workers performed detailed kinetic studies on the mercuration of arenes by Hg(O2CCF3)2. Among others, large primary kinetic isotope effects (KIE) of kH/kD≈6 disclosed in 1967 by Kresge and Brennan already indicated the proton transfer to be rate determining . While previous mechanistic proposals had favored a SEAr-type manifold with discrete σ-complexes,Roberts and co-workers rationalized their observations with transition state 1 featuring a synchronous bond fission and bond formation as illustrated in Figure 1; a SEAr-type mechanism could not completely be ruled out. KIE：动力学同位素效应