光催化环氧化合物的区域选择性开环反应

doi:10.1016/S1872-2067(26)65016-4

摘要/Abstract

摘要： 环氧化合物因其固有的三元环结构带来的环张力和极化的C-O键, 在有机合成中被广泛用作构筑醇、羧酸、烯烃等多种官能化产物的关键合成前体, 因此在药物分子、精细化学品以及功能材料合成中具有重要地位. 经典的环氧化物开环策略多依赖于通过调节反应条件, 实现对环氧环C-O键的选择性活化. 然而, 在底物结构日益复杂、对选择性和绿色性要求不断提高的背景下, 仅依靠传统方式已难以全面满足反应条件温和化、区域选择性可控化及过程可持续化的多重需求. 近年来, 光催化作为一种可持续的新型技术, 能够利用清洁的太阳能激发催化反应体系, 促使环氧化合物C-O键的精准活化与断裂, 为其在温和条件下实现区域选择性开环提供了新的途径.
本综述系统梳理了近年来光催化环氧化合物区域选择性开环反应领域的研究进展. 首先, 简要概述了环氧化合物在酸性和碱性条件下开环位点的差异, 并比较了其在均相光催化与多相光催化两类体系下C-O键断裂的基本作用机制. 随后, 以具体反应类型为主线, 总结了醇解、脱氧、氢解、羧基化、烯丙基化和芳基化等代表性光催化环氧开环反应, 分别归纳了各类反应中关键中间体的形成途径、C-O键断裂方式以及与环氧底物结构和亲核试剂种类之间的关系. 在此基础上, 重点分析了区域选择性调控的核心因素, 包括金属活性中心的电子结构与配位环境、不同金属对氧原子的亲和能力和键能差异, 配体对金属中心电子密度与空间构型的精细调节作用, 亲核试剂的种类及其活化模式, 以及环氧取代基的电子效应和空间位阻对过渡态与中间体稳定性的综合影响, 提出了通过金属位点设计、配体调控和亲核试剂选择以实现区域选择性调控的思路. 最后, 为深化该领域发展并应对当前挑战, 提出了未来研究需着力于以下紧密关联的方向: 一方面, 目前光催化环氧化物开环在活性表征方面仍缺乏统一的量化标准, 亟需建立兼顾活性、选择性和绿色指标的综合评价体系, 并规范光源和反应器等关键信息的记录与共享. 另一方面, 有必要更多依托各类原位和工况表征, 对短寿命自由基、中间体及催化剂表面状态进行直接观测与动态追踪, 以进一步完善C-O键活化机理. 同时, 随着多通道光反应器、自动化操作平台与智能算法的发展, 将光催化环氧化物开环引入机器人和人工智能辅助的高通量筛选框架, 有望显著加快催化剂与反应条件的优化进程, 并为构建系统化数据库提供基础. 最后, 缺乏明显电子导向效应的脂肪族环氧化合物和内位环氧化合物等底物的高效活化, 以及区域选择性与对映选择性的协同调控, 仍是该领域面临的重要挑战, 需通过催化体系精细设计进一步拓展高效转化的底物适用范围. 希望本文能够为推动光催化环氧化合物开环技术向高效率和精准选择性方向发展提供借鉴.

关键词: 开环反应, 环氧化合物, 光催化, 区域选择性, 绿色化学

Abstract: Epoxides boast intrinsic ring strain and high reactivity towards various nucleophiles, thus rendering them fundamental building blocks in organic synthesis. Notably, the ring-opening of these readily available compounds offers a versatile strategy to produce a diverse array of valuable functionalized molecules, such as alcohols, carboxylic acids, olefins, etc. However, the conventional reaction systems for ring-opening typically rely on harmful agents or harsh conditions, which limit their applicability in complex molecule synthesis. Recent advancements in photocatalysis have emerged as a sustainable and promising alternative for precise cleavage of strained C-O bonds in epoxides under mild conditions, showcasing rapid development over the past decade. This mini-review examines the mechanisms and strategies for regioselective epoxide ring-opening triggered by varieties of nucleophiles based on photocatalysis, encompassing fundamental concepts of ring-opening, key factors influencing product regioselectivity and the potential impact of operando techniques and artificial intelligence on this field. The persistent challenges and potential trajectory in this dynamic domain are also critically discussed to foster further innovation.

Key words: Ring-opening, Epoxide, Photocatalysis, Regioselectivity, Green chemistry

李婧宇, 徐艺军. 光催化环氧化合物的区域选择性开环反应[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65016-4.

Jing-Yu Li, Yi-Jun Xu. Regioselective ring-opening of epoxides triggered by light[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65016-4.

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