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

1)用C-F键活化生成二氟亚甲基单元，使p-体系上的三氟甲基选择性脱氟，生成二氟甲基和脱氟三甲基硅烷化合物。特别是有效地合成了二氟烯基硅醚、二氟烯胺和4‘-三氟甲基-1，1-二氟苯基-三甲基硅烷。还原反应在2摩尔当量的金属镁和4摩尔当量的TMS-C_1的作用下，在0℃下反应30min，反应非常顺利。2)合成光学活性含氟氨基酸3，3，3-三氟-2-亚氨基丙酸亚氨基的不对称还原3，3，3-三氟-2-亚氨基丙酸亚胺在3，3，3-三氟乙醇中起着重要的不对称氢化作用。合成了全氟烷基化的α-二亚胺，2，2，3，3，-四氟-1，4-二酮和萜类化合物。通过相应的亚胺基卤化物的钯催化偶联反应合成了新的三氟和全氟烷基α-二亚胺。二亚胺可能是一种很有前途的烯烃聚合催化剂，有待于进一步研究。同样，二氟烯硅醚和三氟甲基酮分别通过铜(II)氧化和锌还原偶联。

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.