美国北卡罗来纳大学Erik J. Alexanian研究小组取得一项新突破。他们开发出光促进的钴催化烯烃和胺合成酰胺的反应。2024年1月5日出版的《科学》发表了这项成果。

在该研究中，该研究团队报道了在温和的条件和低压光促进下，未经修饰的廉价羰基钴催化烯烃氢氨基羰基化反应。反应后硅烷的加入导致一系列钴催化酰胺还原，构成正式的烯烃氢胺甲基化。

这些方法在烯烃和胺组分中表现出很宽的范围，具有高的化学和区域选择性，即使在没有溶剂的情况下也能有效地进行。通过羰基配体的光解作用形成氢化钴被认为导致其在温和条件下的催化活性，这解决了催化领域长期存在的挑战。

据了解，烯烃和胺原料的催化偶联方法在合成化学中具有重要的应用价值。烯烃和胺的直接羰基偶联有希望作为一种完美的原子经济的方法来合成酰胺，但一般的方法仍然不太发达。

附：英文原文

Title: Cobalt-catalyzed synthesis of amides from alkenes and amines promoted by light

Author: Mason S. Faculak, Alexander M. Veatch, Erik J. Alexanian

Issue&Volume: 2024-01-05

Abstract: Catalytic methods to couple alkene and amine feedstocks are valuable in synthetic chemistry. The direct carbonylative coupling of alkenes and amines holds promise as a perfectly atom-economical approach to amide synthesis, but general methods remain underdeveloped. Herein, we report an alkene hydroaminocarbonylation catalyzed by unmodified, inexpensive cobalt carbonyl under mild conditions and low pressure promoted by light. Silane addition after the reaction enables sequential cobalt-catalyzed amide reduction, constituting a formal alkene hydroaminomethylation. These methods exhibit exceptional scope across both alkene and amine components with high chemo- and regioselectivity and proceed efficiently even in the absence of solvent. The formation of a hydridocobalt through photodissociation of a carbonyl ligand is proposed to enable catalytic activity under mild conditions, which addresses a long-standing challenge in catalysis.

DOI: adk2312

Source: https://www.science.org/doi/10.1126/science.adk2312