厦门大学卓春祥团队报道了钼催化炔酮与烯丙胺分子间反应生成苯胺。相关研究成果于2024年9月10日发表在《德国应用化学》。

多取代苯胺类化合物广泛应用于有机合成、药物化学和材料科学中。寻求在简单的反应条件下使用易于获得的起始材料构建这些化合物的各种阵列的稳健有效的方法至关重要。

该文中，研究人员报告了一种前所未有的高效合成2,4-二和2,4,6-三取代苯胺的方法。使用简单的钼（VI）催化剂，从易得的炔酮和烯丙基胺中，以良好到优异的收率有效地制备了各种2,4-二和2,4,6-三取代苯胺。

该方法在几种合成转化、克级反应和生物活性分子衍生化中的应用进一步突显了其合成潜力。初步的机理研究表明，苯胺的形成可能涉及氮杂-迈克尔加成、[1,6]质子转移、环化、脱水、6π-电环化和芳构化的级联反应。

该策略为合成各种有价值的，甚至其中一些在其他方面很难获得的二取代或三取代苯胺提供了一种稳健、简单和模块化的方法。

附：英文原文

Title: Anilines Formation via Molybdenum-Catalyzed Intermolecular Reaction of Ynones with Allylic Amines

Author: Yi-Zhe Yu, Hong-Yi Su, Chun-Xiang Zhuo

Issue&Volume: 2024-09-10

Abstract: The multi-substituted anilines are widely found in organic synthesis, medicinal chemistry and material science. The quest for robust and efficient methods to construct a diverse array of these compounds using readily accessible starting materials under simple reaction conditions is of utmost importance. Here, we report an unprecedented and efficient approach for the synthesis of 2,4-di and 2,4,6-trisubstituted anilines. With a simple molybdenum(VI) catalyst, a wide range of 2,4-di and 2,4,6-trisubstituted anilines were efficiently prepared in generally good to excellent yields from readily accessible ynones and allylic amines. The synthetic potential of this methodology was further underscored by its applications in several synthetic transformations, gram-scale reactions, and derivatization of bioactive molecules. Preliminary mechanistic studies suggested that this aniline formation might involve a cascade of aza-Michael addition, [1, 6]-proton shift, cyclization, dehydration, 6π-electrocyclization, and aromatization. This novel strategy provided a robust, simple, and modular approach for the syntheses of various valuable di- or trisubstituted anilines, some of which were otherwise challenging to access.

DOI: 10.1002/anie.202412299

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202412299