iPRD, School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2-9JT, UK.
Chem Soc Rev. 2014 May 21;43(10):3525-50. doi: 10.1039/c3cs60289c. Epub 2014 Mar 3.
Cu-catalysed arylation reactions devoted to the formation of C-C and C-heteroatom bonds (Ullmann-type couplings) have acquired great importance in the last decade. This review discusses the history and development of coupling reactions between aryl halides and various classes of nucleophiles, focusing mostly on the different mechanisms proposed through the years. Selected mechanistic investigations are treated more in depth than others. For example, evidence in favour or against radical mechanisms is discussed. Cu(I) and Cu(III) complexes involved in the Ullmann reaction and N/O selectivity in aminoalcohol arylation are discussed. A separate section has been dedicated to the synthesis of heterocyclic rings through intramolecular couplings. Finally, recent developments in green chemistry for these reactions, such as reactions in aqueous media and heterogeneous catalysis, have also been reviewed.
在过去的十年中，铜催化的芳基化反应在 C-C 和 C-杂原子键（Ullmann 型偶联）的形成方面变得非常重要。本文综述了芳基卤化物与各种类型亲核试剂之间的偶联反应的历史和发展，重点讨论了多年来提出的不同机制。选择了一些比其他更深入的机制研究。例如，讨论了支持或反对自由基机制的证据。讨论了 Ullmann 反应中涉及的 Cu(I)和 Cu(III)配合物以及氨基醇芳基化中的 N/O 选择性。专门有一个部分用于通过分子内偶联合成杂环环。最后，还综述了这些反应在绿色化学方面的最新进展，例如在水介质中的反应和多相催化。
