Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Gava Zang, Zanjan, Iran.
School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan.
Org Biomol Chem. 2022 Mar 23;20(12):2500-2507. doi: 10.1039/d2ob00037g.
A highly chemo- and stereoselective synthesis of diethyl ()-2-(alkylidene)-2-phosphonoacetonitriles the Knoevenagel condensation reaction of carbonyl compounds with diethyl cyanomethylphosphonate in the presence of zinc chloride has been achieved. By the presented method, various -isomers of arylmethylidene phosphonates rather than Horner-Wadsworth-Emmons olefination products were obtained in good to excellent yields. Their configurations were determined by X-ray diffraction and NMR analyses. In addition, DFT calculations provided insights into the chemo- and stereoselectivity of the reaction.
一种高度化学选择性和立体选择性的合成（外消旋）-2-（亚烷基）-2-膦酰基乙腈的方法是通过羰基化合物与氰基甲基膦酸二乙酯在氯化锌存在下的 Knoevenagel 缩合反应实现的。通过所提出的方法，可以以良好至优异的收率获得各种芳基亚甲基膦酸酯的 -异构体，而不是 Horner-Wadsworth-Emmons 烯烃产物。它们的构型通过 X 射线衍射和 NMR 分析确定。此外，DFT 计算提供了对反应的化学选择性和立体选择性的深入了解。
