南京师范大学韩维课题组近日成功利用含铁催化剂实现了芳烃的C-H键羟基化。2021年10月1日出版的《科学》杂志发表了这项成果。

在该文中，研究人员报道了一种受生物启发的L-半胱氨酸衍生配体，它与铁形成的配合物可以催化以过氧化氢作为末端氧化剂的无定向芳烃碳-氢键羟基化反应。该反应以其广泛的底物范围、优异的选择性和良好的产率为特点，并显示出与氧化敏感官能团，如醇、多酚、醛，甚至硼酸的兼容性。该方法适用于通过多次碳-氢键羟基化合成多酚类化合物，以及天然产物和药物分子的后期功能化。

研究人员表示，芳烃的可持续、无定向和选择性催化羟基化反应一直是一个研究挑战，这是由于芳烃碳-氢键的相对惰性、酚类产物的较高反应活性导致副产物过度氧化，以及该反应经常缺乏区域选择性。

附：英文原文

Title: Iron-catalyzed arene CH hydroxylation

Author: Lu Cheng, Huihui Wang, Hengrui Cai, Jie Zhang, Xu Gong, Wei Han

Issue&Volume: 2021-10-01

Abstract: The sustainable, undirected, and selective catalytic hydroxylation of arenes remains an ongoing research challenge because of the relative inertness of aryl carbon-hydrogen bonds, the higher reactivity of the phenolic products leading to over-oxidized by-products, and the frequently insufficient regioselectivity. We report that iron coordinated by a bioinspired L-cystine–derived ligand can catalyze undirected arene carbon-hydrogen hydroxylation with hydrogen peroxide as the terminal oxidant. The reaction is distinguished by its broad substrate scope, excellent selectivity, and good yields, and it showcases compatibility with oxidation-sensitive functional groups, such as alcohols, polyphenols, aldehydes, and even a boronic acid. This method is well suited for the synthesis of polyphenols through multiple carbon-hydrogen hydroxylations, as well as the late-stage functionalization of natural products and drug molecules.

DOI: abj0731

Source: https://www.science.org/doi/10.1126/science.abj0731