Progress ofα-Position Functionalization of Ethers under Photo/Electrocatalysis

Abstract

Ethers are widely used in organic chemistry, materials science, biomedicine and other fields due to their excellent physicochemical properties. Among them, tetrahydrofuran/tetrahydrothiophene and their derivatives are the core backbones for building biologically active molecules and complex natural products. In recent years, photo/electrocatalysis has gradually become an important tool for chemists to synthesize novel compounds due to its compliance with the requirements of green chemistry and the unique pathway that mostly involves radical intermediates. The functionalization of α-positions of ethers using photo/electrocatalysis is a green and efficient synthetic strategy. Therefore, the research progress of photo/electrocatalytic functionalization of ether compounds at the α-position is reviewed with ether/sulfide as examples, and a detailed description of some of the mechanisms is provided. Keywords ethers; photocatalysis; electrocatalysis; photoelectric co-catalysis; functionalization 醚类化合物因为其具有优异的物理化学性质在自 然界中扮演着重要的角色. 其中, 四氢呋喃/噻吩被广泛 应用于众多领域 [1][2][3] , 特别是在药物化学, 许多天然产物 存在着四氢呋喃/噻吩结构单元, 包括木脂素 [4] 、聚醚类 抗生素 [5] 等, 这些物质具有多种生物活性, 包括抗肿瘤、 抗过敏、抗疟疾以及抗微生物等. 然而, 较高的键解离 能 [6] (BDE＝384.92 kJ/mo)、低极性的 α-位碳氢键和较高 的氧化电位 [7] (E 1/2 red ＝＋1.75 V vs SCE for THF)使得直 接活化四氢呋喃的 α-位碳氢键成为挑战 [8][9][10][11] .碳氢键的官能团化引起了化学家们极大的关注, 因