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正卤素等氧化剂反应，生成C-S键被削弱的硫离子，容易发生亲核取代反应。70%Hf/Py和Bu_4NH_2F_3的氟离子取代硫生成有机氟化合物。通过这种方式，三氟甲基取代的芳烃和烯烃、三氟甲醚、三氟甲胺、α-氟硫化物和可视二氟烯烃可以很容易地从相应的有机硫前体中获得。(2)与有机硅化合物的交叉偶联反应这种新的反应现在被称为Hiyama偶联。虽然三甲基硅基与乙烯基硅烷有关，但SiFMe_2或SiF_2Me对于一般的烯基硅烷是必需的。烷氧基硅烷也是适用的。作为偶联伙伴，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在钯催化剂上进行二聚氧化。有机锡化合物与有机锡化合物的交叉偶联和碳锡化。在一种由钯和亚氨基膦配体组成的新型催化剂上，有机锡化合物很容易发生交叉偶联反应、氧化二聚反应和碳锡化反应生成乙炔。

(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.