无金属、温和条件下，通过分子氧氧化 C-C 键断裂，构建 1,3,4-噁二唑-2(3H)-酮。

A metal-free and mild approach to 1,3,4-oxadiazol-2(3H)-ones via oxidative C-C bond cleavage using molecular oxygen.

机构信息

College of Pharmacy, Research Institute of Pharmaceutical sciences, Seoul National University, 1 Gwanak-ro, Gwa-nak-gu, Seoul 08826, Korea.

Department of Medicinal Bioscience, College of Interdisciplinary & Creative Studies, Konyang University, 121 Daehak-ro, Nonsan, Chungnam, Korea.

出版信息

Org Biomol Chem. 2018 Mar 28;16(12):2105-2113. doi: 10.1039/c7ob03188b. Epub 2018 Mar 7.

DOI:10.1039/c7ob03188b

PMID:29511752

Abstract

A mild metal-free approach to 1,3,4-oxadiazol-2(3H)-ones via 1,3,4-oxadiazin-5(6H)-ones is described. This novel transformation, promoted by the electron-withdrawing p-substituents on the phenyl group at the α-carbonyl position, features a tandem reaction consisting of oxidative hydroxylation and C-C bond cleavage using molecular oxygen. The method utilizes KCO in CHCN without any oxidants, transition metals, or additives, enabling the tunable synthesis of 1,3,4-oxadiazin-5(6H)-ones, 1,3,4-oxadiazol-2(3H)-ones, and α-ketoamides under mild aerobic conditions.

摘要

通过 1,3,4-噁二唑-2(3H)-酮描述了一种温和的无金属方法来制备 1,3,4-噁二唑-2(3H)-酮。这种新颖的转化反应，由α-羰基位置上苯基的吸电子 p-取代基促进，通过分子氧进行串联反应，包括氧化羟化和 C-C 键断裂。该方法使用 KCO 在 CHCN 中进行，无需任何氧化剂、过渡金属或添加剂，可在温和的有氧条件下实现 1,3,4-噁二唑-2(3H)-酮、1,3,4-噁二唑-2(3H)-酮和α-酮酰胺的可调合成。