电催化功能基团耐受型 Shono 环氨基甲酸酯氧化反应及胺氧自由基介导作用
Electrochemical Functional-Group-Tolerant Shono-type Oxidation of Cyclic Carbamates Enabled by Aminoxyl Mediators.
机构信息
Department of Chemistry, University of Wisconsin-Madison, Madison, WI, 53706, USA.
出版信息
Angew Chem Int Ed Engl. 2018 May 28;57(22):6686-6690. doi: 10.1002/anie.201803539. Epub 2018 May 2.
Abstract
An electrochemical method has been developed for α-oxygenations of cyclic carbamates by using a bicyclic aminoxyl as a mediator and water as the nucleophile. The mediated electrochemical process enables substrate oxygenation to proceed at a potential that is approximately 1 V lower than the redox potential of the carbamate substrate. This feature allows for functional-group compatibility that is inaccessible with conventional Shono oxidations, which proceed by direct electrochemical substrate oxidation. This reaction also represents the first α-functionalization of non-activated cyclic carbamates with oxoammonium oxidants.
摘要
电化学方法已被开发用于环状碳酸酯的α-氧代反应，使用双环氨基氧作为介体，水作为亲核试剂。该介导电化学过程使底物的氧代反应能够在比碳酸酯底物的氧化还原电位低约 1 V 的电势下进行。这一特点使得与传统的 Shono 氧化反应相比具有官能团兼容性，后者通过直接电化学底物氧化进行。该反应还代表了首次使用氧铵氧化剂对非活化环状碳酸酯进行α-功能化。
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2
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