【作者】 张娟；

【导师】 梁福顺；

【作者基本信息】 东北师范大学 ， 有机化学， 2013， 硕士

【摘要】 α-氧代酰胺是天然产物中具有生物活性的中间体，也是重要的有机合成中间体。因其独特的药物和生理活性， α-氧代酰胺类化合物引起了有机化学家和药物化学家们的极大关注。鉴于α-氧代酰胺的重要性，其合成方法得到快速发展。我们发展了一种简单、方便、高效的合成-氧代酰胺的新方法。该方法在铜、NIS和空气的存在下，从简单的甲基酮和胺出发，合成了一系列α-氧代酰胺化合物，避免了传统方法中使用高价催化剂和苛刻条件，并可进行较大剂量的反应。最佳反应条件为：2.2当量的胺、1.2当量的NIS、溶剂为甲苯，室温敞口体系。研究发现，当甲基酮芳环上的取代基为吸电子基时，产率较高；为供电子基时，产率下降。杂环类底物也得到了较好的反应结果。考察了胺的范围，伯胺和仲胺的反应都能较好进行，仲胺产率较高，伯胺产率相对较低。伯胺在得到-氧代酰胺的同时也生成酰胺副产物。详细研究了反应的机理。-氧代酰胺和酰胺的形成归因于过氧四元环的不同的开环消除方式。反应的显著特点是廉价的催化剂，易得的起始原料，温和的条件（室温），利用空气作为氧源。本反应机理的提出对铜催化有氧氧化合成-氧代酰胺机理研究是一个很好的补充。更多还原

【Abstract】 The-ketoamides are natural products possessing biological activity. They arealso important intermediates in organic synthesis. Because of its unique pharmacuticaland physiological activity, α-ketoamides attract great interest to organic chemists andmedicinal chemists. In view of the importance of the α-ketoamides, quite a lot ofsynthetic methods has been developed.We have developed a simple, convenient and efficient method toward thesynthesis of-ketoamides. In the presence of copper catalyst, the simple methylketone reacted with amine and NIS in the air, affording a series of α-ketoamides. Thisprotocol avoided the use of expensive catalyst and harsh conditions generally adoptedin the conventional method, and could be conducted in gram scale. The optimizedreaction conditions were as follows:2.2equivalents of amine,1.2equivalents of NIS,toluene as the solvent, at room temperature and in the open air. It was found that,when acetophenone substituents are electron-withdrawing groups, the yields arehigher. While the yields decrease slightly when the substituents on the aryl rings areelectron-donating groups. The heterocyclic substrates also gave satisfactory results,but with relatively lower yields. The scope of amine component was also examined.Both the primary and secondary amines were efficient for the reaction. The yields ofthe secondary amines are higher, the corresponding yields decreased for the primaryamines. Reactions with primary amines produced-ketoamides and amideby-products. Copper-catalyzed aerobic oxidation mechanism for the formation ofα-ketoamides was proposed. The reaction features inexpensive catalyst, readilyavailable starting materials, mild conditions (room temperature), the use of air as themolecular oxygen source (not oxygen balloon).更多还原