C-H键活化,chemical review概论
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（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
deuterium facilitate pyrazole borate pronounced carbazole isotopic ubiquitous be restricted to cesium stand out alkali metal pivalate diastereoseletive endothermic exothermic formate alkyne annulation
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
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.
displacement 取代，移位
in situ
在反应过程中
dual
双重的
dimer
二聚体
sodium
钠
triflate
三氟甲磺酸
bicarbonate 碳酸氢盐
carbonate 碳酸盐
noteworthy 值得注意的
heteroatom 杂原子
hydrocarbon 烃类来自百度文库
imido
酰亚胺
New words and phrases：
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
温和
ambient
周围环境
pyrrole
吡咯
proceed
开始，继续进行
readily
容易地
favorable 有利的
analogous 类似的
stoichiometric arene complexes with respect to dimeric optically active orthoslope entropy acetate crystallographic precursor agostic interaction acidity facile hence c.p. exceedingly
isoproypyl
异丙基
bidentate
双齿的
piralic
特戊酸
biaryl
联芳
potassium
钾
revisit
再论
azole
唑
elusive
难懂的
robustness
稳健性
triazole
三唑
ortho-
邻位的
meta-
间位的
para-
对位的
CONTENTS
1. Introduction 2. Stoichiometric C-H Bond Metalation
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.
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
异羟肟酸
main group
主族
rcedox
氧化还原反应
predominatly
占据主导
unravel
阐明
electron-withdrawing 吸电子
Lutz Ackermann*, Chem. Rev.2011, 111, 1315–1345
Carboxylate-Assisted Transition-MetalCatalyzed C-H Bond Functionalizations: Mechanism and Scope
New words and phrases：
2.1. Intermolecular Metalation 2.2. Stoichiometric Cyclometalations 2.3. Related Assisted Metalations with Monodentate Bases
3. Catalytic C-H Bond Functionalizations
1.INTRODUCTION
➢ oxidative addition with electronrich latetransition metals
➢ σ-bond metathesis with early transition metals
➢ electrophilic activation with electrondeficient late transition metals
3 Traditional modes:
➢ oxidative addition with electronrich latetransition metals ➢ σ-bond metathesis with early transition metals ➢ electrophilic activation with electrondeficient late transition metals
deuterium facilitate pyrazole borate pronounced carbazole isotopic ubiquitous be restricted to cesium stand out alkali metal pivalate diastereoseletive endothermic exothermic formate alkyne annulation
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
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.
displacement 取代，移位
in situ
在反应过程中
dual
双重的
dimer
二聚体
sodium
钠
triflate
三氟甲磺酸
bicarbonate 碳酸氢盐
carbonate 碳酸盐
noteworthy 值得注意的
heteroatom 杂原子
hydrocarbon 烃类来自百度文库
imido
酰亚胺
New words and phrases：
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
温和
ambient
周围环境
pyrrole
吡咯
proceed
开始，继续进行
readily
容易地
favorable 有利的
analogous 类似的
stoichiometric arene complexes with respect to dimeric optically active orthoslope entropy acetate crystallographic precursor agostic interaction acidity facile hence c.p. exceedingly
isoproypyl
异丙基
bidentate
双齿的
piralic
特戊酸
biaryl
联芳
potassium
钾
revisit
再论
azole
唑
elusive
难懂的
robustness
稳健性
triazole
三唑
ortho-
邻位的
meta-
间位的
para-
对位的
CONTENTS
1. Introduction 2. Stoichiometric C-H Bond Metalation
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.
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
异羟肟酸
main group
主族
rcedox
氧化还原反应
predominatly
占据主导
unravel
阐明
electron-withdrawing 吸电子
Lutz Ackermann*, Chem. Rev.2011, 111, 1315–1345
Carboxylate-Assisted Transition-MetalCatalyzed C-H Bond Functionalizations: Mechanism and Scope
New words and phrases：
2.1. Intermolecular Metalation 2.2. Stoichiometric Cyclometalations 2.3. Related Assisted Metalations with Monodentate Bases
3. Catalytic C-H Bond Functionalizations
1.INTRODUCTION
➢ oxidative addition with electronrich latetransition metals
➢ σ-bond metathesis with early transition metals
➢ electrophilic activation with electrondeficient late transition metals