Zhao Bao-Yin, Jia Qiong, Wang Yong-Qiang
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, School of Foreign Languages, Northwest University, Xi'an, 710069, China.
Nat Commun. 2024 Mar 18;15(1):2415. doi: 10.1038/s41467-024-46576-2.
Phenols and anilines are of extreme importance for medicinal chemistry and material science. The development of efficient approaches to prepare both compounds has thus long been a vital research topic. The utility of phenols and anilines directly reflects the identity and pattern of substituents on the benzenoid ring. Electrophilic substitutions remain among the most powerful synthetic methods to substituted phenols and anilines, yet in principle achieving ortho- and para-substituted products. Therefore, the selective preparation of meta-substituted phenols and anilines is the most significant challenge. We herein report an efficient copper-catalyzed dehydrogenation strategy to exclusively synthesize meta-carbonyl phenols and anilines from carbonyl substituted cyclohexanes. Mechanistic studies indicate that this transformation undergoes a copper-catalyzed dehydrogenation/allylic hydroxylation or amination/oxidative dehydrogenation/aromatization cascade process.
酚类和苯胺类化合物在药物化学和材料科学中极为重要。因此，开发高效制备这两类化合物的方法长期以来一直是一个至关重要的研究课题。酚类和苯胺类化合物的用途直接反映了苯环上取代基的特性和模式。亲电取代反应仍然是合成取代酚类和苯胺类化合物最有效的方法之一，但原则上只能得到邻位和对位取代产物。因此，选择性制备间位取代的酚类和苯胺类化合物是最重大的挑战。我们在此报告了一种高效的铜催化脱氢策略，可从羰基取代的环己烷中专门合成间位羰基酚类和苯胺类化合物。机理研究表明，这种转化过程经历了铜催化的脱氢/烯丙基羟基化或胺化/氧化脱氢/芳构化级联反应。
