Catalytic Reactions Directed by a Structurally Well-Defined Aminomethyl Cyclopalladated Complex,Accounts of Chemical Research

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Catalytic Reactions Directed by a Structurally Well-Defined Aminomethyl Cyclopalladated Complex
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2021-11-11 , DOI: 10.1021/acs.accounts.1c00365
Haocheng Zhang ₁ , Tianxiao Jiang ₁ , Jingyun Zhang ₁ , Hanmin Huang ₁

Affiliation

The introduction of N-containing moieties into feedstock molecules to build nitrogenated functional molecules has always been widely studied by the organic chemistry community. Progress in this field paves new roads to the synthesis of N-containing molecules, which are of significant importance in biological activities and play vital roles in pharmaceuticals and functional materials. Remarkable progress has been achieved in the field of transition metal-catalyzed C–N bond-forming reactions, typified by alkene hydroamination and the aza-Wacker reaction. However, the poisoning effect of electron-donating amine substrates on late transition metal catalysts presents a key impediment to these reactions, thus limiting the scope of amine substrates to electron-deficient amide derivatives. To address this problem, our group developed a palladium–aminomethyl complex with a three-membered palladacycle structure that allowed for the incorporation of electron-rich amine building blocks via C–C bond instead of C–N bond construction. This Account details the discovery of the well-defined aminomethyl cyclopalladated complex and recapitulates its applications for the catalysis of a series of aminomethylation reactions. We highlight how the understanding of the fundamental structural properties of the defined complex guided us toward tuning the reactivity of nucleophiles to initiate aminomethylation in different modes. Moreover, principles of designing and establishing further cascade reactions are also described.

中文翻译：

由结构明确的氨基甲基环钯络合物引导的催化反应

将含氮部分引入原料分子以构建氮化功能分子一直受到有机化学界的广泛研究。该领域的进展为含氮分子的合成开辟了新的道路，这些分子在生物活性中具有重要意义，在药物和功能材料中发挥着重要作用。在以烯烃加氢胺化和氮杂-瓦克反应为代表的过渡金属催化的 C-N 键形成反应领域取得了显着进展。然而，给电子胺底物对后过渡金属催化剂的毒害效应是这些反应的关键障碍，因此将胺底物的范围限制在缺电子酰胺衍生物上。为了解决这个问题，我们小组开发了一种具有三元钯环结构的钯-氨甲基配合物，允许通过 C-C 键而不是 C-N 键结构引入富电子胺结构单元。该帐户详细介绍了定义明确的氨甲基环钯络合物的发现，并概括了其在催化一系列氨甲基化反应中的应用。我们强调了对定义的复合物基本结构特性的理解如何引导我们调整亲核试剂的反应性以在不同模式下启动氨基甲基化。此外，还描述了设计和建立进一步级联反应的原理。

更新日期：2021-12-07

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