Department of Chemistry, Indian Institute of Technology Patna , Bihta 801103, Bihar, India.
J Org Chem. 2016 Dec 16;81(24):12247-12257. doi: 10.1021/acs.joc.6b02176. Epub 2016 Nov 23.
A straightforward method is developed in this paper for the synthesis of α-ketoesters through copper-catalyzed aerobic oxidation of (hetero)aryl acetimidates using molecular oxygen as a sustainable oxidant. The reaction represents the first example of the direct synthesis of aryl-α-ketoesters from arylacetimidates through the aerobic oxidation of a benzylic C-H (C═O) bond in moderate to good yield. This transformation occurs under mild reaction conditions with a wide range of substrates and utilizes a readily available oxidant and catalyst. The synthetic utility of this transformation is demonstrated through scaled-up synthesis. A plausible reaction mechanism is also proposed.
本文开发了一种通过铜催化（杂）芳基乙内酰脲的有氧氧化，使用分子氧作为可持续氧化剂合成α-酮酯的直链方法。该反应代表了通过芳基乙内酰脲的有氧氧化，以中等到良好的收率，直接合成芳基-α-酮酯的首例。该转化在温和的反应条件下，具有广泛的底物范围，并利用易得的氧化剂和催化剂进行。通过放大合成证明了这种转化的合成实用性。还提出了一个合理的反应机理。
