Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, 305-8571, Japan.
Chemistry. 2018 Dec 5;24(68):17932-17935. doi: 10.1002/chem.201805054. Epub 2018 Nov 7.
The selective activation of one C-F bond (single activation) of the CF group on cyclopropanes was achieved for the first time. When (trifluoromethyl)cyclopropanes were treated with arenes, allylsilanes, silyl enol ethers, or hydrosilanes in the presence of Me AlCl, fluoride elimination and the subsequent ring opening proceeded to afford 4,4-difluorohomoallylated products. In the absence of external nucleophiles, an alkyl group of AlR was effectively introduced to provide the corresponding 1,1-difluoroalkenes.
首次实现了对环丙烷上 CF 基团的一个 C-F 键（单键活化）的选择性活化。当（三氟甲基）环丙烷在 MeAlCl 的存在下与芳烃、烯丙基硅烷、硅基烯醇醚或硅氢化氢反应时，氟化物消除和随后的开环反应进行，得到 4,4-二氟同烯丙基化产物。在没有外部亲核试剂的情况下，AlR 的烷基有效地被引入，提供了相应的 1,1-二氟烯烃。
