Abstract

Amination and amidation of aryl compounds using a transition-metal-catalyzed cross-coupling reaction typically involves prefunctionalization or preoxidation of either partner. In recent years, a new class of transition-metal-catalyzed cross-dehydrogenative coupling reaction has been developed for the direct formation of aryl C–N bonds. This short review highlights the substantial progress made for ortho-C–N bond formation via transition-metal-catalyzed chelation-directed aryl C–H activation and gives an overview of the challenges that remain for directed meta- and para-selective reactions.

1 Introduction

2 Intramolecular C–N Cross-Dehydrogenative Coupling

2.1 Nitrogen Functionality as Both Coupling Partner and Directing Group

2.2 Chelating-Group-Directed Intramolecular C–N Bond Formation

3 Intermolecular C–N Cross-Dehydrogenative Coupling

3.1 ortho-C–N Bond Formation

3.1.1 Copper-Catalyzed Reactions

3.1.2 Other Transition-Metal-Catalyzed Reactions

3.2 meta- and para-C–N Bond Formation

4 C–N Cross-Dehydrogenative Coupling of Acidic C–H Bonds

5 Conclusions

Amination and amidation of aryl compounds using a transition-metal-catalyzed cross-coupling reaction typically involves prefunctionalization or preoxidation of either partner. In recent years, a new class of transition-metal-catalyzed cross-dehydrogenative coupling reaction has been developed for the direct formation of aryl C–N bonds. This short review highlights the substantial progress made for ortho-C–N bond formation via transition-metal-catalyzed chelation-directed aryl C–H activation and gives an overview of the challenges that remain for directed meta- and para-selective reactions.

1 Introduction

2 Intramolecular C–N Cross-Dehydrogenative Coupling

2.1 Nitrogen Functionality as Both Coupling Partner and Directing Group

2.2 Chelating-Group-Directed Intramolecular C–N Bond Formation

3 Intermolecular C–N Cross-Dehydrogenative Coupling

3.1 ortho-C–N Bond Formation

3.1.1 Copper-Catalyzed Reactions

3.1.2 Other Transition-Metal-Catalyzed Reactions

3.2 meta- and para-C–N Bond Formation

4 C–N Cross-Dehydrogenative Coupling of Acidic C–H Bonds

5 Conclusions

中文翻译：

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过渡金属催化的定向芳基C–H / N–H交叉偶联反应的最新进展

摘要

使用过渡金属催化的交叉偶联反应对芳基化合物进行胺化和酰胺化通常涉及任何一个配偶体的预官能化或预氧化。近年来，为了直接形成芳基C–N键，已经开发出了一类新型的过渡金属催化的交叉脱氢偶联反应。此短审查亮点方面取得重大进展邻通过过渡金属催化的螯合定向芳基C-H活化，并给出了其保持用于定向的挑战的概述-C-N键形成的元-和对位-选择性的反应。

1引言

2分子内C–N交叉脱氢偶联

2.1作为联轴器合作伙伴和指导小组的氮功能

2.2螯合基团指导的分子内C–N键的形成

3分子间C–N交叉脱氢偶联

3.1 邻-C–N键形成

3.1.1铜催化的反应

3.1.2其他过渡金属催化的反应

3.2 间-和对-C-N键的形成

4 C–N酸性C–H键的交叉脱氢偶联

5。结论

使用过渡金属催化的交叉偶联反应对芳基化合物进行胺化和酰胺化通常涉及任何一个配偶体的预官能化或预氧化。近年来，为了直接形成芳基C–N键，已经开发出了一类新型的过渡金属催化的交叉脱氢偶联反应。此短审查亮点方面取得重大进展邻通过过渡金属催化的螯合定向芳基C-H活化，并给出了其保持用于定向的挑战的概述-C-N键形成的元-和对位-选择性的反应。

1引言

2分子内C–N交叉脱氢偶联

2.1作为联轴器合作伙伴和指导小组的氮功能

2.2螯合基团指导的分子内C–N键的形成

3分子间C–N交叉脱氢偶联

3.1 邻-C–N键形成

3.1.1铜催化的反应

3.1.2其他过渡金属催化的反应

3.2 间-和对-C-N键的形成

4 C–N酸性C–H键的交叉脱氢偶联

5。结论