Development of Novel Synthetic Reactions Based on the Activation of the Third Row Elements'

(1)氧化脱硫氟化有机硫化合物与带正电的卤素等氧化剂反应后，生成C-S键弱的硫离子，容易发生亲核取代。70% HF/Py和Bu_4NH_2F_3的氟离子取代硫生成有机氟化合物。这样，三氟甲基取代的芳烃和烯烃、三氟甲基醚、三氟甲基胺、-氟硫化物和可见二氟烯烃很容易从相应的有机硫前体中得到。(2)与有机硅化合物的交叉偶联反应这种新反应现在被称为Hiyama偶联。虽然三甲基硅基与乙烯基硅烷有关，但对于烯基硅烷，通常需要SiFMe_2或SiF_2 Me。烷氧基硅烷也适用。作为偶联剂，芳基氯化物现在被证明是适用的。现在在DMF中实现了从硅到铜(I)的金属转化。因此，炔基硅烷与卤苯偶联或使用钯催化剂氧化二聚体。与氢硅烷共轭还原α、β不饱和酯和酮。(3)有机锡化合物的交叉偶联和羧基化使用一种由钯和亚氨基膦配体组成的新型催化剂，有机锡化合物很容易发生交叉偶联反应、氧化二聚化和羧基化成乙炔。

(1) Oxidative Desulfurization FluorinationUpon reaction with an oxidant like a positive halogen, organosulfur compounds gives sulfonium ions whose C-S bonds are weaked to undergo nucleophilic substitution readily. A fluoride ion of 70% HF/Py and Bu_4NH_2F_3 replaces sulfur to give organofluorine compounds. In this way, trifluoromethyl-substituted aromatics and olefins, trifluoromethyl ethers, trifluoromethylamines, alpha-fluoro sulfides, and vis-difluoro olefins are shown to be readily available from the corresponding organosulfur precursors.(2) Cross-Coupling Reactions with Organosilicon CompoundsThis novel reaction is now called as the Hiyama Coupling. Although a trimethylsilyl group is pertinent to vinylsilanes, SiFMe_2 or SiF_2 Me is necessary for alkenylsilanes in general.Alkoxysilanes also are applicable. As a coupling partner, aryl chlorides are now shown to be applicable.Transmetalation from silicon to copper(I) is now achieved in DMF.Thus, alkynylsilanes couple with halobenzenes or dimerizes oxidatively using a palladium catalyst. Conjugate reduction of alpha, beta-unsaturated esters and ketones is attained with hydrosilanes.(3) Cross-Coupling and Carbostannylation with Organotin CompoundsUsing a novel catalyst consisting of palladium and an imino phosphine ligand, organotin compounds are shown to readily undergo cross-coupling reactions, oxidative dimerization, and carbostannylation to acetylenes.