Fang Mougui, Wu Pingjie, Wang Xia, Xie Ziyue, Hou Yali, Liu Yao, Wu Jingjing, Wu Fanhong
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
Shanghai Engineering Research Center of Green Fluoropharmaceutical Technology, Shanghai Institute of Technology, Shanghai 201418, China.
J Org Chem. 2022 Mar 18;87(6):4107-4111. doi: 10.1021/acs.joc.1c02908. Epub 2022 Feb 24.
A novel asymmetric copper-catalyzed intermolecular cyanobenzoyldifluoromethylation of alkenes with iododifluoromethyl ketones and TMSCN has been reported, which provides a particularly valuable route to access chiral β-difluoroacyl nitriles with excellent enantioselectivities. The method permits the efficient cyanation of varied β-difluoroacyl-benzylic radicals in mild conditions with high functional group tolerance. The reaction proceeds through a radical pathway. In order to get insight into the stereochemical outcome, computational mechanistic studies were conducted.
据报道，一种新型的不对称铜催化烯烃与碘二氟甲基酮和TMSCN的分子间氰基苯甲酰基二氟甲基化反应，为获得具有优异对映选择性的手性β-二氟酰基腈提供了一条特别有价值的途径。该方法能够在温和条件下，以高官能团耐受性实现各种β-二氟酰基苄基自由基的高效氰化反应。该反应通过自由基途径进行。为了深入了解立体化学结果，进行了计算机理研究。
