可见光促进的氧原子α位c-oxygen atom alpha position c promoted by visible light.docx

可见光促进的氧原子?位 C-H 键官能团化反应研究中文摘要中文摘要近年来，很多文献报道了可见光促进的 N-?-sp3 C-H 键官能团化的反应，受到 了化学家们的广泛关注。然而，关于 O-?-sp3 C-H 键官能团化的报道仍然比较少。 氧的孤对电子比较稳定，很难被激发态的光敏剂氧化，无法通过 SET（single electron transfer，单电子转移）过程实现 O-?-sp3 C-H 键的官能团化。我们利用三氯化碳自 由基来攫取苄位的氢原子，通过 HAT（hydrogen atom transfer，氢原子转移）过程， 从而达到 O-?-sp3 C-H 键官能团化的目的。本论文的主要工作就是在可见光催化的 条件下，利用 HAT 过程实现 O-?-sp3 C-H 键的官能团化。本文主要分为四个部分：第一章，综述了 O-?-sp3 C-H 键官能团化反应的研究进展和可见光促进的O-?-sp3 C-H 键官能团化反应的研究进展。第二章，利用可见光催化 O-?-sp3 C-H 键官能团化，达到了苄基烷基醚一步酯 化的目的。主要研究了在三氯溴甲烷和光敏剂 Ir(dtb-bpy)(ppy)2PF6 的共同作用下， 苄基烷基醚与乙酸乙酯发生酯交换反应，得到相应的酯化产物。该反应从来没有 被报道过。第三章，可见光促进的苄基烷基醚直接被氧化为芳香醛或酮。在该反应中， 苄基烷基醚是一个隐藏的羰基结构。在光敏剂 Ir(dtb-bpy)(ppy)2PF6 的作用下，该反 应实现了苄基烷基醚的氧化断裂，得到羰基化合物。第四章，可见光促进的二醇的单官能团化反应。该反应体系经过?-溴代缩醛， 将二醇的两个羟基一步转化为不同的官能团。关键词：可见光催化，O-?-sp3 C-H键官能团化，Ir(dtb-bpy)(ppy)2PF6，苄基烷 基醚，?-溴代醚，?-溴代缩醛作者：卢平 指导教师：李丕旭副教授英文摘要可见光促进的氧原子?位 C-H 键官能团化反应研究Investigation of Photoredox O-?-sp3 C-H Cleavage ReactionsAbstractThe research on functionalization of N-?-sp3 C-H has attracted interest from many organic chemists in recent years. However, the functionalization of O-?-sp3 C-H bonds is still less reported. The lone pair electrons of oxygen are too stable to be oxidized by the excited photosensitizer. It is very difficult to achieve functionalization of O-?-sp3 C-H bonds through single electron transfer process. We successfully realized O-?-sp3 C-H bonds cleavage by utilizing the ·CCl3 radical generated under visible-light photoredox conditions to abstract the hydrogen of the benzyl position, through the hydrogen atom transfer. Several practical organic reactions were developed based on the finding.This paper is divided into four parts:The first chapter is a summary of the O-?-sp3 C-H functionalization reactions and the visible-light-mediated O-?-sp3 C-H functionalization reactions.The second chapter is about visible light catalytic O-?-sp3 C-H functionalization reaction of benzyl alkyl ethers to form esters. We investigated the reaction between alkyl benzyl ethers and ethyl acetate. Transesterifica