Cai Shoule, Zhao Zeyu, Yang Guoqing, Huang Hanmin
Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of China, Hefei, P. R. China.
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal University, Huaibei, P. R. China.
Nat Chem. 2024 Dec;16(12):1972-1981. doi: 10.1038/s41557-024-01673-z. Epub 2024 Nov 18.
Precisely differentiating chemicals featuring minor discrepancies is the prerequisite for achieving high selectivities in both chemical synthesis and biological activities. However, efficient strategies to differentiate and sort such congeneric compounds are lacking, posing daunting challenges for synthetic endeavours aimed at their orderly incorporation. Here we report a dynamic amine-sorting strategy that incorporates the chemoselective formation of the aminomethyl cyclopalladated complex to achieve the efficient differentiation of amine congeners. A series of amines sharing similar three-dimensional structures and properties, as well as possessing notoriously strong binding ability to metals, can be efficiently differentiated, enabling the highly chemo-, regio- and enantioselective multicomponent aminomethylamination of dienes to construct a variety of unsymmetrical chiral diamines. This dynamic amine-sorting strategy tackles the long-standing challenge of precise differentiation and orderly incorporation of aliphatic amines with subtle differences. From a broader perspective, the success demonstrates that meticulously designed metal complexes can provide flexible and general solutions for controlling delicate selectivities in sophisticated synthesis.
精确区分存在细微差异的化学物质是在化学合成和生物活性方面实现高选择性的前提条件。然而，目前缺乏有效区分和分类此类同系化合物的策略，这给旨在将它们有序引入的合成工作带来了艰巨挑战。在此，我们报告了一种动态胺分类策略，该策略通过化学选择性形成氨基甲基环钯配合物来实现胺同系物的高效区分。一系列具有相似三维结构和性质、且对金属具有极强结合能力的胺能够被有效区分，从而实现二烯的高度化学、区域和对映选择性多组分氨基甲基化反应，构建多种不对称手性二胺。这种动态胺分类策略解决了长期以来精确区分和有序引入具有细微差异的脂肪胺的挑战。从更广泛的角度来看，这一成功表明精心设计的金属配合物可为复杂合成中控制精细选择性提供灵活通用的解决方案。
