Organocatalytic cascade reactions represent a powerful strategy for the rapid construction of complex chiral molecules with multiple stereocenters from simple substrates under mild conditions. The intriguing structural feature and diverse reactivity of catalytically generated dienolate species render them competent and versatile intermediates for the development of practical and valuable cascade reactions. Over the past years, a plethora of innovative and pioneering noncovalent ammonium dienolate-mediated cascade reactions have been designed and implemented under the catalysis of chiral organocatalysts, making dienolate activation a general, robust, and complementary method for the functionalization of unsaturated carbonyl compounds and related substances. This review illustrates the recent advances in organocatalytic noncovalent ammonium dienolate-mediated cascade reactions (mainly from 2010 to 2023), including the cascade transformations of ammonium dienolates directly generated from unsaturated ketone/aldehyde, ester/lactone/azlactone, amide/lactam/pyrazolone/oxindole, and alkylidene nitrile compounds. The contents are arranged based on the reaction types of the ammonium dienolates, with an emphasis on cascade 2,5-, 3,5-, and 4,5-difunctionalizations of these intermediates. Furthermore, other cascade reactions involving the 1,3-, 2,3-, and even more complex 3,4,5-reactivities of ammonium dienolates were also discussed. The reaction pathway, reaction stereoinduction, and synthetic applications of the ammonium dienolate-mediated cascade reactions were highlighted throughout the article. As a stimulating and ever-growing research area, the organocatalytic noncovalent ammonium dienolate-mediated cascade reactions are expected to continue demonstrating their magic power for constructing chiral targets in the future and further expanding the boundaries of asymmetric catalysis.

有机催化级联反应代表了在温和条件下从简单底物快速构建具有多个立构中心的复杂手性分子的强大策略。催化生成的二烯醇化物具有有趣的结构特征和多样化的反应性，使其成为开发实用且有价值的级联反应的有力且多功能的中间体。在过去的几年里，在手性有机催化剂的催化下，人们设计并实现了大量创新和开创性的非共价二烯醇铵介导的级联反应，使二烯醇化活化成为不饱和羰基化合物及相关化合物功能化的通用、稳健和补充的方法。物质。本文综述了有机催化非共价二烯醇铵介导的级联反应的最新进展（主要是2010年至2023年），包括由不饱和酮/醛、酯/内酯/吖内酯、酰胺/内酰胺/吡唑啉酮/直接生成二烯醇铵的级联转化。羟吲哚和亚烷基腈化合物。内容根据二烯醇铵的反应类型排列，重点是这些中间体的级联2,5-、3,5-和4,5-双官能化。此外，还讨论了涉及二烯醇铵的 1,3-、2,3- 甚至更复杂的 3,4,5- 反应性的其他级联反应。整篇文章重点介绍了二烯醇铵介导的级联反应的反应途径、反应立体诱导和合成应用。 作为一个令人兴奋且不断发展的研究领域，有机催化非共价二烯醇铵介导的级联反应有望在未来继续展示其构建手性靶标的魔力，并进一步拓展不对称催化的边界。