4-二甲氨基吡啶催化的芳基α-卤代酯无金属有氧氧化制备芳基α-酮酯
4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters.
作者信息
Jung Yeonghun, Hong Jee Eun, Baek Seung Tae, Hong Suckchang, Kwak Jae-Hwan, Park Yohan
机构信息
College of Pharmacy, Inje Institute of Pharmaceutical Sciences and Research, Inje University, 197 Inje-ro, Gimhae, Gyeongnam 50834, Republic of Korea.
College of Pharmacy, Research Institute of Pharmaceutical Sciences, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea.
出版信息
ACS Omega. 2020 Sep 2;5(36):22951-22957. doi: 10.1021/acsomega.0c02511. eCollection 2020 Sep 15.
A novel, metal-free aerobic oxidation method is described. 4-Dimethylaminopyridine (DMAP) successfully catalyzed the oxidation of aryl α-halo esters to corresponding aryl α-keto esters (up to 95% yield) under mild reaction conditions (LiCO, dimethylacetamide, air, and room temperature). A mechanism has been proposed where the oxidation proceeds through a [3 + 2] cycloaddition between O in an air atmosphere and pyridinium ylides. The ylides are supposedly generated from aryl α-halo esters and DMAP in the presence of carbonates. Based on the plausible mechanism, the potential of DMAP as a catalyst in oxidation reactions was extended.
描述了一种新型的无金属需氧氧化方法。在温和的反应条件下（碳酸锂、二甲基乙酰胺、空气和室温），4-二甲基氨基吡啶（DMAP）成功催化芳基α-卤代酯氧化为相应的芳基α-酮酯（产率高达95%）。有人提出了一种机理，即氧化反应通过在空气气氛中O与吡啶叶立德之间的[3 + 2]环加成进行。叶立德据推测是在碳酸盐存在下由芳基α-卤代酯和DMAP生成的。基于这一合理的机理，扩展了DMAP作为氧化反应催化剂的潜力。
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