Laboratory of Organic Synthesis, Bio and Organocatalysis, Chemistry Department, Universidad de los Andes , Cra 1 No. 18A-12 Q:305, Bogotá 111711, Colombia.
J Org Chem. 2014 May 16;79(10):4544-52. doi: 10.1021/jo500562w. Epub 2014 May 5.
The highly efficient transamidation of several primary, secondary, and tertiary amides with aliphatic and aromatic amines (primary and secondary) is described. The reaction is performed in the presence of a 5 mol % concentration of different hydrated salts of Fe(III), and the results show that the presence of water is crucial. The methodology was also applied to urea and phthalimide to demonstrate its versatility and wide substrate scope. An example of its use is an intramolecular application in the synthesis of 2,3-dihydro-5H-benzo[b]-1,4-thiazepin-4-one, which is the bicyclic core of diltiazem and structurally related drugs (Budriesi, R.; Cosimelli, B.; Ioan, P.; Carosati, E.; Ugenti, M. P.; Spisani, R. Curr. Med. Chem. 2007, 14, 279-287). A plausible mechanism that explains the role of water is proposed on the basis of experimental observations and previous mechanistic suggestions for transamidation reactions catalyzed by transition metals such as copper and aluminum. This methodology represents a significant improvement over other existing methods; it can be performed in air and with wet or technical grade solvents.
描述了几种伯、仲和叔酰胺与脂肪族和芳香族胺（伯胺和仲胺）的高效转酰胺反应。该反应在不同水合铁(III)盐的 5 mol%浓度下进行，结果表明水的存在是至关重要的。该方法还应用于脲和邻苯二甲酰亚胺，以证明其通用性和广泛的底物范围。其用途的一个例子是在合成 2,3-二氢-5H-苯并[b]-1,4-噻嗪-4-酮中的分子内应用，该化合物是地尔硫䓬和结构相关药物的双环核心（Budriesi，R.；Cosimelli，B.；Ioan，P.；Carosati，E.；Ugenti，M. P.；Spisani，R. Curr. Med. Chem. 2007, 14, 279-287）。基于实验观察和以前关于铜和铝等过渡金属催化的转酰胺反应的机理建议，提出了一种解释水作用的合理机制。该方法优于其他现有方法，它可以在空气和湿的或工业级溶剂中进行。
