Equipe Synthèse Organique et Phytochimie, Institut de Chimie, CNRS-UdS, UMR 7177, 4 rue Blaise Pascal, CS 90032, 67081, Strasbourg, France.
Chimie ParisTech, PSL University, CNRS, Institute of Chemistry for Life and Health Sciences, Chemical Theory and Modelling Group, F-75005, Paris, France.
Chemistry. 2022 Jan 3;28(1):e202103598. doi: 10.1002/chem.202103598. Epub 2021 Dec 9.
A copper-mediated coupling reaction between ynamides and diazo-compounds to produce N-allenamides is reported for the first time. This method enables facile and rapid access to terminal N-allenamides by using commercially available TMS-diazomethane with wide functional group compatibility on the nitrogen. Furthermore, the ubiquity of molecules containing a fluorine moiety in medicine, in agricultural, and material science requires the continuous search of new building blocks, including this unique surrogate. The CuI/diazo protocol was successfully applied to the synthesis of fluorine-substituted N-allenamides. DFT calculations provided insights in the mechanism involved.
首次报道了铜介导的炔酰胺和重氮化合物之间的偶联反应，生成 N-烯丙酰胺。该方法使用商业可得的 TMS-重氮甲烷，通过氮上广泛的官能团兼容性，可方便、快速地获得末端 N-烯丙酰胺。此外，在医药、农业和材料科学中，含有氟原子的分子无处不在，这就需要不断地寻找新的砌块，包括这种独特的替代物。CuI/重氮议定书成功地应用于氟取代 N-烯丙酰胺的合成。DFT 计算提供了对所涉及机制的深入了解。
