铜催化空气氧化选择性断裂乙二醇醚中饱和c-c键的分析-analysis of selective cleavage of saturated c - c bond in ethylene glycol ether by copper-catalyzed air oxidation.docx

II II Copper-Catalyzed Aerobic Oxidative Cleavage of C(sp3)-C(sp3) Bond of Glycol Ethers Abstract The thesis demonstrates an unexpected Cu-catalyzed coupling reaction of carboxylic acids and aldehydes with glycol ethers via aerobic oxidative cleavage of the C(sp3)- C(sp3) bond in glycol ethers, which can be utilized to prepare α-acyloxy ethers. Under the typical reaction conditions, the saturated C-C bond could be selectively cut off using oxygen or air as the stoichiometric oxidant, which would exhibit a novel protocol for C(sp3)-C(sp3) bond activation. It is divided into three chapters as followings: The first chapter summarizes the recent developments of transition metal-catalyzed oxidative cleavage of C-C bond. Especially, this section will be focused on the transition metal catalyzed aerobic oxidative cleavage of C-C bond. The second chapter shows in detail the Cu-catalyzed coupling reaction of carboxylic acid with glycol ethers, whose C-C bond is oxidative cleavaged by molecular oxygen. This chapter introduces the significance of the reaction, the reaction condition optimization and the substrate scope. The reaction mechanism is discussed at last. The third chapter discusses in detail the Cu-catalyzed coupling reaction of aldehydes with glycol ethers, whose C-C bond is oxidative cleavaged by molecular oxygen. It also describes in detail the reaction condition optimization and the substrate scope. The reaction mechanism is discussed at last. At last, we summarize the significance of coupling reaction of carboxylic acids /aldehydes with glycol ethers. We also describe the potential value of the reaction and overlook it. Key Words: Copper Catalysis; Oxidation Reaction; C-C Bond; Cleavage; Glycol Ether PAGE PAGE IV 目录 摘要 II HYPERLINK \l _bookmark0 Abstract II HYPERLINK \l _bookmark1 第一章 综述 1 HYPERLINK \l _bookmark2 1.1 引言 1 HYPERLINK \l _bookmark3 1.2 过渡金属催化的 C-C 单键断裂反应的研究进展 1 HYPERLINK \l _bookmark4 1.2.1 简单饱和环烷烃 C-C 单键的断裂反应 1 HYPERLINK \l _bookmark5