Frey Johanna, Goddard Jean-Philippe, Cormier Morgan
Laboratoire d'Innovation Moléculaire et Applications (LIMA), UMR 7042, Université de Haute-Alsace (UHA), Université de Strasbourg, CNRS, Mulhouse 68100, France.
J Org Chem. 2024 Oct 18;89(20):15217-15224. doi: 10.1021/acs.joc.4c02009. Epub 2024 Oct 7.
Dicobalt hexacarbonyl complexes are well-known for their applications in the Nicholas reaction or simply as a protecting group for alkynes. To recover the alkyne, demetalation is necessary, which usually involves a stoichiometric amount of an oxidizing agent or a strong ligand. This article reports a demetalation methodology based on a photocatalytic process. This approach employs a photocatalyst under aerobic conditions, and the optimal results were achieved using mild near-infrared irradiation. A mechanistic investigation is also presented to elucidate how the photocatalytic system promotes this deprotection. This tool is compatible with the one-pot reaction and orthogonal deprotection of alkynes, offering new perspectives for further applications.
二钴六羰基配合物因其在尼古拉斯反应中的应用或简单地作为炔烃的保护基团而闻名。为了回收炔烃,脱金属是必要的,这通常需要化学计量的氧化剂或强配体。本文报道了一种基于光催化过程的脱金属方法。该方法在有氧条件下使用光催化剂,在温和的近红外照射下取得了最佳效果。还进行了机理研究,以阐明光催化体系如何促进这种脱保护反应。该方法与炔烃的一锅反应和正交脱保护兼容,为进一步应用提供了新的视角。