SYNTHESIS OF NOVEL FLUORINATED COMPOUNDS BY THE USE OF ACTIVE FLUORINATING REAGENTS

1)C-F键活化生成二氟亚甲基结构单元研究开发了从p-体系上连接的三氟甲基选择性脱氟，生成二氟亚甲基和脱氟三甲基硅基甲基化合物。特别地，已经有效地制备了二氟烯醇甲硅烷基醚、二氟烯胺和4’-三氟甲基-1，1-二氟苄基三甲基硅烷。2摩尔当量的金属镁和4摩尔当量的TMS-Cl在0℃下反应30 min，还原反应进行得非常顺利1，实现了工业上可行的制备二氟乙烯基单体二氟乙烯基隆和八氟[2.2]对环芳烷氟代亚芳基聚合物的方法。2）光学活性含氟氨基酸的合成3-三氟-2-亚氨基丙酸酯是在3，3，3-三氟乙醇中通过钯催化还原反应合成的。4-二酮和频哪醇。新的三氟和全氟烷基-α-通过钯催化的相应的亚胺基卤化物的偶联反应有效地制备了二亚胺。二亚胺是一种很有前途的烯烃聚合催化剂，值得进一步研究。同样，二氟烯醇甲硅烷基醚和三氟甲基酮已被耦合的Cu（II）氧化和Zn还原，分别。

1) C-F bond activation for the creation of difluoromethylene units Selective defluorination from trifluoromethyl group attached to p-system leading to the formation of difluoromethylene and defluorotrimethylsilylmethyl compounds has been developed. In particular, difluoroenolsilyl ethers, difluoroenamines, and 4'-trfluoromethy1, 1-difluorobenzy1 trimethylsilane nave been effectively prepared. The reductive reaction proceeded very smoothy1 by the action of two mole equivalents of metallic magnesium and four mole equivalents of TMS-C1 at 0℃ for 30 min. The industrially feasible production of difluorovinyl monomer for difluorovinyron and octafluoro [2.2 paracyclophane for flurorinated perarylene polymer would be realized.2) Synthesis of optically active fluorinated amino acids Asymmetric reduction of imino group of 3, 3, 3-trifluoro-2-iminopropanoates was achieved by palladium catalyzed reduction in 3, 3, 3-trifluoroethanol which played an essentially important role for the asymmetric hydrogenation.Syntheses of perfluoroalkylated α-diimines, 2, 2, 3, 3,-tetrafluoro-1, 4-diketones and pinacols.Novel trifluoro- and perfluoroalkyl-α-diimines have been efficiently prepared by the palladium catalyzed coupling reaction of the corresponding imidoyl halides. The diimines could be a promising catalyst for polymerization of alkenes which would be studied in future. Likewise, difluoroenolsilyl ethers and trifluoromethyl ketones have been coupled by Cu (II) oxidation and Zn reduction, respectively.