中国科学技术大学黄汉民团队报道了实现不对称手性二胺多选择性构建的动态胺分选策略。相关研究成果发表在2024年11月18日出版的《自然—化学》。

精确区分具有微小差异的化学物质，是在化学合成和生物活性中实现高选择性的先决条件。然而，目前缺乏区分和分类此类同系物的有效策略，这对旨在有序掺入此类化合物的合成工作构成了严峻的挑战。

该文中，研究人员报告了一种结合了氨基甲基环钯络合物的，化学选择性形成的动态胺分选策略，以实现胺同系物的有效区分。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，可以被有效区分，使二烯的高度化学、区域和对映选择性多组分氨基甲基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。

附：英文原文

Title: Dynamic amine sorting enables multiselective construction of unsymmetrical chiral diamines

Author: Cai, Shoule, Zhao, Zeyu, Yang, Guoqing, Huang, Hanmin

Issue&Volume: 2024-11-18

Abstract: 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.

DOI: 10.1038/s41557-024-01673-z

Source: https://www.nature.com/articles/s41557-024-01673-z