华东师范大学姜雪峰团队报道了光催化C-F水裂解活化羟基化反应。相关研究成果发表在2024年4月9日出版的国际学术期刊《美国化学会杂志》。

C–F键是碳中心键中最强的共价单键（126 kcal/mol），其中氟的最高电负性（χ=4）产生了最短的键长（1.38Å）和最小的范德华半径（r_w=1.47Å），这给活化和转化带来了巨大的挑战。

该文中，C–F转化是通过光铀催化未活化的芳基氟化物的羟基化实现的，在环境条件下使用水作为羟基源递送多功能酚。活化的特征是单电子转移（SET）/氢原子转移（HAT）/氧原子转移（OAT）的级联序列，与激发的铀酰阳离子高度整合。*UO₂²⁺促使水在温和的光激发下分解，在关键的OAT过程中以过氧桥接的方式锁住活性氧，并通过HAT过程释放氢气。

附：英文原文

Title: Photouranium-Catalyzed C–F Activation Hydroxylation via Water Splitting

Author: Xiu Zhao, Leiyang Bai, Jiayi Li, Xuefeng Jiang

Issue&Volume: April 9, 2024

Abstract: The C–F bond is the strongest covalent single bond (126 kcal/mol) in carbon-centered bonds, in which the highest electronegativity of fluorine (χ = 4) gives rise to the shortest bond length (1.38 ) and the smallest van der Waals radius (rw = 1.47 ), resulting in enormous challenges for activation and transformation. Herein, C–F conversion was realized via photouranium-catalyzed hydroxylation of unactivated aryl fluorides using water as a hydroxyl source to deliver multifunctional phenols under ambient conditions. The activation featured cascade sequences of single electron transfer (SET)/hydrogen atom transfer (HAT)/oxygen atom transfer (OAT), highly integrated from the excited uranyl cation. The *UO22+ prompted water splitting under mild photoexcitation, caging the active oxygen in a peroxo-bridged manner for the critical OAT process and releasing hydrogen via the HAT process.

DOI: 10.1021/jacs.3c13908

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c13908