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.

苯酚及其衍生物在自然界中普遍存在，是极其重要的工业化学品。它们的特性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、对位定向效应，间位取代的苯酚历来更难合成。在这里，我们描述了一种转置苯酚的过程，该过程取决于相应邻醌的区域选择性重氮化。该过程直接从其更常见和易获得的对位取代异构体中提供间位取代苯酚，并表现出良好的化学选择性，使其能够在后期环境中应用。通过改变 OH 基团的电子效应及其氢键轨迹，我们的转座可用于使天然产物和现有化学库多样化，并有可能缩短生产代表性不足的芳烃异构体的时间和成本。