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.

精确区分具有微小差异的化学品是在化学合成和生物活性中实现高选择性的前提。然而，缺乏区分和分类此类同源化合物的有效策略，这给旨在有序掺入的合成工作带来了艰巨的挑战。在这里，我们报道了一种动态胺分选策略，该策略结合了氨基甲基环钯酸盐复合物的化学选择性形成，以实现胺同系物的有效分化。可以有效地区分一系列具有相似三维结构和性质的胺，以及众所周知的与金属的强结合能力，使二烯烃的高度化学、区域和对映选择性多组分氨基甲基胺化能够构建各种不对称的手性二胺。这种动态胺分选策略解决了精确区分和有序掺入具有细微差异的脂肪胺的长期挑战。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以为控制复杂合成中的精细选择性提供灵活和通用的解决方案。