Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China.
Institute of Pharmacology, Pharmacy College, Shandong First Medical University & Shandong Academy of Medical Sciences, Tai'an 271016, P. R. China.
J Org Chem. 2020 Oct 2;85(19):12670-12681. doi: 10.1021/acs.joc.0c01842. Epub 2020 Sep 14.
A novel route for ruthenium(II)-catalyzed α-fluoroalkenylation of oxime ethers with -difluorostyrenes C-H activation and C-F cleavage has been developed for the first time. Notably, the alkenyl units of products exhibit exclusive Z-configuration. This reaction features a broad substrate scope and good functional group tolerance. A plausible reaction mechanism is confirmed by an available cycloruthenated intermediate. Besides, the -methyl oximyl-directing group can be readily removed to access the α-fluoroalkenylated acetophenones.
首次开发了一种新型的钌（II）催化肟醚与 -二氟苯乙烯的 α-氟烯基化反应途径，涉及 C-H 活化和 C-F 断裂。值得注意的是，产物的烯基单元具有独特的 Z-构型。该反应具有广泛的底物范围和良好的官能团耐受性。通过可用的环钌化中间体证实了一个合理的反应机制。此外，-甲基肟基导向基团可以很容易地去除，从而得到 α-氟烯基化的苯乙酮。
