铜(Ⅱ)配合物催化Chan-Lam偶联反应研究进展

Recent Progress on Chan-Lam Coupling Reactions Catalyzed by Copper(Ⅱ) Complexes

铜催化的Chan-Lam偶联反应是一种高效构建C—N、C—O和C—S键的重要方法,具有条件温和、底物范围广及产率高等优点,在有机合成、药物化学和材料科学等领域有着广泛的应用.虽然有大量铜盐或铜盐/配体组合催化的Chan-Lam反应被报道,但具有明确分子结构铜(II)配合物催化的Chan-Lam反应研究相对较少.近年来,含不同配体铜(II)配合物催化的Chan-Lam反应吸引了合成化学家们的关注,取得了一定的成就.一部分结构新颖的铜配合物被设计合成出来,并用作芳基硼酸与多种亲核体Chan-Lam偶联反应的催化剂.从均相催化和异相催化两方面综述了铜配合物催化Chan-Lam偶联反应的最新研究进展,均相催化部分按铜配合物配位方式的不同加以分类,非均相催化部分按时间先后予以阐述,并对不同课题组提出的Chan-Lam偶联反应机理进行了梳理分析,最后展望了该研究领域的未来发展前景.

Copper-catalyzed Chan-Lam reaction represents an important and highly efficient method for the synthesis of organic molecules containing carbon-heteroatom(C—N, C—O, C—S) bonds, which has many advantages such as mild conditions, wide substrates range and high yields. Therefore, the Chan-Lam coupling reactions are extensively applied in organic synthesis, medicinal chemistry and material science, etc. Although many catalytic systems using different copper salt alone or in combination with various ligands for Chan-Lam coupling reaction have been extensively reported by different groups, the studies on the Chan-Lam coupling reaction employing well-defined copper complexes as catalysts were underdeveloped. In recent years, the Chan-Lam reactions catalyzed by copper complexes with different ligands have attracted more special attention from synthetic chemist and made many achievements. Some novel copper complexes have been designed and synthesized,which were further used as efficient catalysts for Chan-Lam coupling reactions of arylboronic acids with various nucleophiles.The recent progresses on Chan-Lam coupling reactions catalyzed by well-defined copper(II) complexes are summarized from two aspects of homogeneous catalysis and heterogeneous catalysis in detail. Then the homogeneous Chan-Lam reactions are classified by the different coordination mode of copper complexes, and the heterogeneous Chan-Lam reactions are described according to chronological order. The reaction mechanism on Chan-Lam coupling proposed by different research groups is also straightened out and discussed. Finally, the development prospects of this research field are pointed out.