School of Chemistry and Chemical Engineering, Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi University, North Fourth Road, Shihezi, Xinjiang 832003, People's Republic of China.
College of Chemistry, Center of Computational Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China.
J Org Chem. 2021 Feb 5;86(3):2339-2358. doi: 10.1021/acs.joc.0c02478. Epub 2021 Jan 7.
The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings of traditional methods. The broad scope of substrates in transition metal catalyzed amidations remains a challenge. Here, a manganese(I)-catalyzed method for the direct synthesis of amides from a various number of esters and amines is reported with unprecedented substrate scope using a low catalyst loading. A wide range of aromatic, aliphatic, and heterocyclic esters, even in fatty acid esters, reacted with a diverse range of primary aryl amines, primary alkyl amines, and secondary alkyl amines to form amides. It is noteworthy that this approach provides the first example of the transition metal catalyzed amide bond forming reaction from fatty acid esters and amines. The acid-base mechanism for the manganese(I)-catalyzed direct amidation of esters with amines was elucidated by DFT calculations.
过渡金属催化酯与胺的酰胺键形成反应已被开发为克服传统方法缺点的一种先进方法。在过渡金属催化酰胺化中，广泛的底物范围仍然是一个挑战。在此，报道了一种使用低催化剂负载量的锰（I）催化方法，可直接合成各种数量的酯和胺的酰胺，具有前所未有的底物范围。广泛的芳香族、脂肪族和杂环酯，甚至脂肪酸酯，都能与各种芳基伯胺、伯烷基胺和仲烷基胺反应生成酰胺。值得注意的是，该方法提供了第一个从脂肪酸酯和胺合成酰胺键的过渡金属催化反应的例子。通过 DFT 计算阐明了锰（I）催化酯与胺的直接酰胺化的酸碱机理。
