加拿大麦吉尔大学Lumb, Jean-Philip团队报道了苯酚的对位-间位异构化。相关研究成果发表在2024年4月17日出版的《自然—化学》。

苯酚及其衍生物在自然界中普遍存在，也是至关重要的工业化学品。它们的性质与芳环的相对取代模式密切相关，反映了众所周知的OH基团的电子效应。由于这些邻位、对位导向效应，间位取代酚在历史上更难合成。

该文中，研究人员描述了一种转换酚类的过程，该过程取决于相应的邻醌的区域选择性重氮化。该方法直接从其更常见和可获得的对位取代异构体中获得间位取代苯酚，并显示出良好的化学选择性，使其能够在后期应用。通过改变OH基团的电子效应及其氢键轨迹，盖换位可以用于使天然产物和现有化学库多样化，并可能缩短生产代表性不足的芳烃异构体的长度和成本。

附：英文原文

Title: A para- to meta-isomerization of phenols

Author: Edelmann, Simon, Lumb, Jean-Philip

Issue&Volume: 2024-04-17

Abstract: Phenols and their derivatives are ubiquitous in nature and critically important industrial chemicals. Their properties are intimately linked to the relative substitution pattern of the aromatic ring, reflecting well-known electronic effects of the OH group. Because of these ortho-, para-directing effects, meta-substituted phenols have historically been more difficult to synthesize. Here we describe a procedure to transpose phenols that hinges on a regioselective diazotization of the corresponding ortho-quinone. The procedure affords the meta-substituted phenol directly from its more common and accessible para-substituted isomer, and demonstrates good chemoselectivity that enables its application in late-stage settings. By changing the electronic effect of the OH group and its trajectory of hydrogen bonding, our transposition can be used to diversify natural products and existing chemical libraries, and potentially shorten the length and cost of producing underrepresented arene isomers.

DOI: 10.1038/s41557-024-01512-1

Source: https://www.nature.com/articles/s41557-024-01512-1