摘要/Abstract

含氧结构骨架普遍存在于天然产物和生物活性小分子中，同时在有机合成中是一类重要的合成子，因此，含氧化合物的合成一直是科学研究的热点.过渡金属催化氧气氧插入反应策略是一类新颖而又高效构建碳碳键和碳杂键的方法.随着该类方法的应用和发展，它已成为含氧杂原子化合物最重要的合成方法之一.在前人的工作基础上，同时结合本课题组之前的工作，探讨了氧气环境条件下过渡金属催化醛酮类、烯炔烃、芳烃类及杂环芳烃类等参与的氧插入反应及其在合成醇类、酯类、酰胺类和含氧杂环类等领域的新应用；综述了基于C—H键活化以及C—C键断裂等方式参与过渡金属催化氧气氧插入反应过程的研究新进展.过渡金属催化剂在氧气氧化下，可以引发氧自由基历程的氧插入反应，并实现氧自由基的高效和高选择性插入.该类反应具有条件温和、操作简单、绿色环保和高原子经济性等特点.
关键词: 过渡金属催化, 氧气氧化, C—H活化, C—C断裂, 氧插入反应, 自由基历程
Oxygen-bearing structures are attractive synthetic targets due to their wide presence in a great number of natural products and biologically active molecules, and their role as useful synthons in organic synthesis. Thus, the preparation of O-bearing compounds has been an important topic. Transition metal-catalyzed aerobic oxygenation strategy has emerged as a novel and efficient methodology for constructing C-C bonds and C-heteroatom bonds. This strategy has become one of the most important and useful synthetic method in organic synthesis of O-bearing compounds. Based on the previous work of our group and others, herein, the new applications of transition metal-catalyzed oxygenation of C-H bond activation and C-C bond cleavage with oxygen as oxygen source are discussed. The recent progress in trans-metal catalytic oxygen insertion of ketones, aldehydes, alkene, alkynes, arene and aromatic heterocyclic compounds has been reviewed. Transition metal-catalysts can initiate oxygen insertion reaction of free radical pathway and realize selective insertion of oxygen radicals under oxygen oxidation. These reactions are characterized by mild conditions, environmental protection and highly atom economy.
Key words: transition metal catalysis, oxygen oxidation, C-H activation, C-C cleavage, oxygenated reaction, radical pathway


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