过渡金属催化与电化学的结合已成为有机合成的有力工具,因为催化剂可以控制反应性和选择性。然而,由于电极钝化、二聚化和过氧化,将催化剂与阳极氧化产生的烷基自由基物种偶联仍然具有挑战性。
该文中,研究人员开发了聚合配对电解法,用于镍催化剂与由光诱导环状醇和铁催化剂金属电荷转移配体衍生的烷基自由基的偶联,为酮的位点特定和远程芳基化提供了一种实用的方法。光催化与会聚配对电解的协同使用,可以为金属催化的自由基偶联反应提供替代途径。
附:英文原文
Title: Synergistic use of photocatalysis and convergent paired electrolysis for nickel-catalyzed arylation of cyclic alcohols
Author: Cong Ma, Zhiwei Zuo, Tian-Sheng Mei
Issue&Volume: 2024/04/16
Abstract: The merging of transition metal catalysis with electrochemistry has become a powerful tool for organic synthesis because catalysts can govern the reactivity and selectivity. However, coupling catalysts with alkyl radical species generated by anodic oxidation remains challenging because of electrode passivation, dimerization, and overoxidation. In this study, we developed convergent paired electrolysis for the coupling of nickel catalysts with alkyl radicals derived from photoinduced ligand-to-metal charge-transfer of cyclic alcohols and iron catalysts, providing a practical method for site-specific and remote arylation of ketones. The synergistic use of photocatalysis with convergent paired electrolysis can provide alternative avenues for metal-catalyzed radical coupling reactions.
DOI: 10.1016/j.scib.2024.04.031
Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927324002652
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