厦门大学黄培强团队报道了阳离子铱配合物催化还原酯的胺化和串联胺化-烷基化。相关研究成果发表在2024年12月10日出版的《德国应用化学》。

该文报道了一种方便有效的一锅催化还原胺化方法，以及对实验室稳定且易得的常见羧酸酯，进行官能化的第一种多组分串联还原胺化反应。该方法基于阳离子[Ir(COD)₂]BArF催化的酯的化学选择性硅氢化反应，然后是一锅酸介导的胺化和亲核加成反应。

反应在温和条件下以非常低的催化剂负载量（0.1 mol%的Ir）进行，如15g规模的反应所示，催化剂负载量可以进一步降低到0.001 mol%。该方法用途广泛，能够使用含或不含α-质子的酯进行伯胺和仲胺的N-单烷基化，以生产各种仲胺和叔胺，以及α-支化/官能化胺。

该方法具有高度的化学选择性，可以耐受各种官能团，如溴、三氟甲基、酯和氰基。该方法的价值，通过一步催化合成两种生物相关的N-单甲基α-氨基酯，和抗帕金森病药物吡贝地尔，以及使用两种短链甘油三酯作为烷基化原料，得到了证明。

附：英文原文

Title: Catalytic Reductive Amination and Tandem Amination–Alkylation of Esters Enabled by a Cationic Iridium Complex

Author: Guang-Sheng Lu, Zhong-Lei Ruan, Yan Wang, Jin-Fang Lü, Jian-Liang Ye, Pei-Qiang Huang

Issue&Volume: 2024-12-10

Abstract: Reported herein is a convenient and efficient method for one-pot, catalytic reductive amination, as well as the first multi-component tandem reductive amination - functionalization of bench-stable and readily available common carboxylic esters. This method is based on the cationic [Ir(COD)2]BArF-catalyzed chemoselective hydrosilylation of esters, followed by one-pot acid-mediated amination and nucleophilic addition. The reaction was conducted under mild conditions at a very low catalyst loading (0.1 mol% of Ir), which could be further reduced to 0.001 mol%, as demonstrated by a reaction at a 15 g scale. The method is highly versatile, allowing the use of esters with or without α-protons for the N-mono-alkylation of primary and secondary amines to produce diverse secondary and tertiary amines, as well as α-branched/functionalized amines. The method is highly chemoselective and tolerates a variety of functional groups such as bromo, trifluoromethyl, ester, and cyano groups. The value of the method was demonstrated by the one-step catalytic synthesis of two bio-relevant N-mono-methyl α-amino esters and the antiparkinsonian agent piribedil, as well as by the use of two shorter chain triglycerides as alkylating feedstock.

DOI: 10.1002/anie.202422742

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202422742