The discovery of the copper-promoted Chan-Lam coupling reaction with boronic acids more than ten years ago has greatly advanced the carbon-heteroatom cross-coupling chemistry. The N-arylation/O-arylation methodology is now a powerful new synthetic tool, made even more attractive by the mild conditions required. Significant progress has been made in expanding the scope and the applications as well as understanding the mechanism of this reaction. This review includes an examination of various C-X cross-couplings using boronic acids and their derivatives, and a survey of the mechanistic studies that have been carried out.

1 General Introduction

2 C-N Cross-Coupling

2.1 Original NH-Containing Substrates

2.2 Factor Xa Inhibitors

2.3 Selective N-Arylation of Nucleobases

2.4 Additional NH-Containing Substrates

3 C-O Cross-Coupling

3.1 Intermolecular C-O Cross-Coupling

3.2 Intramolecular C-O Cross-Coupling

4 Substrate Selectivity and Reactivity

5 Applications in Solid-Phase Synthesis

6 C-N and C-O Cross-Coupling with Boronic Acid Derivatives

6.1 Boroxines, Boronic Esters, and Trifluoroborate Salts

6.2 Alkenylboronic Acids and Alkynylboronic Acids

6.3 Alkylboronic Acids

7 C-S and C-Se/C-Te Cross-Coupling

8 C-Cl, C-Br, and C-I Cross-Coupling

9 C-C and C-H Cross-Coupling

10 Mechanistic Considerations

10.1 Empirical Observations

10.2 General Mechanistic Observations

10.3 Mechanistic Study of the Catalytic Reaction

11 Other Transition Metals

12 Other Organometalloids

13 Conclusion

Chan-Lam coupling - copper-promoted - carbon-heteroatom­ cross-coupling - boronic acids - N-arylation

十多年前，铜促进的Chan-Lam与硼酸的偶联反应的发现极大地推动了碳-杂原子交叉偶联化学的发展。N-芳基化/ O-芳基化方法现已成为一种功能强大的新合成工具，由于所需的温和条件而变得更具吸引力。在扩大范围和应用以及理解该反应机理方面已取得重大进展。这篇综述包括对使用硼酸及其衍生物的各种CX交叉偶联的研究，以及对已经进行的机理研究的综述。

1一般介绍

2 CN交叉耦合

2.1原始的含NH的底物

2.2 Xa因子抑制剂

2.3核糖核酸酶的选择性N-化

2.4其他含NH的底物

3 CO交叉耦合

3.1分子间CO交叉耦合

3.2分子内CO交叉偶联

4底物的选择性和反应性

5在固相合成中的应用

6 CN和CO与硼酸衍生物的交叉偶联

6.1硼氧烷，硼酸酯和三氟硼酸盐

6.2烯基硼酸和炔基硼酸

6.3烷基硼酸

7 CS和C-Se / C-Te交叉耦合

8 C-Cl，C-Br和CI交叉耦合

9 CC和CH交叉耦合

10个机械注意事项

10.1实证观察

10.2一般机械观测

10.3催化反应机理

11种其他过渡金属

12其他有机金属

13结论

Chan-Lam偶联-铜促进的-碳-杂原子交叉偶联-硼酸-N-芳基化