Transition Metal Catalyzed Addition Reactions of Heteroatom Elements

含硫、硒、磷或胂（第15族和第16族元素）的有机杂原子化合物是一类在药物和材料开发中有用的化合物。因此，开发有效的合成方法是有机合成的一项重要任务。这些化合物是由有机卤素化合物与由单质硫或磷制备的各种杂原子试剂的取代反应制备的。然而，这些方法通常使用有毒试剂和严格的反应条件来去除微量的氧气或水分，并形成金属卤化物作为副产物。本项目的目的是利用单质硫或磷与不饱和化合物加成反应，开发经济、环保的有机杂原子化合物合成方法。研究了有机二硫化物的S-S键裂解反应，发现铑配合物催化二硫化物交换反应。该催化剂还能够在有机多硫化物和单质硫之间交换硫原子。结果表明，铑配合物可用于单质硫的活化。该方法可应用于有机二硫化物与有机二硒化物的交换反应。有机二硫化物、二硒化物和1-炔在铑配合物存在下的反应选择性地生成硒代硫代炔。结果表明，过渡金属配合物可以区分硫原子和硒原子。提出了一种催化三苯基膦与乙烯、丙烯或1-丁烯加成得到1-烷基膦盐的方法。目前的研究表明，过渡金属配合物可以有效地用于有机硫和有机磷化合物的各种转化。

Organoheteroatom compounds containing sulfur, selenium, phosphorous, or arsine (group 15 and 16 elements) are a group of useful compounds in the development of drugs and materials. It is therefore an important task of organic synthesis to develop effective synthetic methods for the compounds. Such compounds have been prepared by using the substitution reactions of organohalogen compounds with various heteroatom reagents, which were prepared from elemental sulfur or phosphorous. The methods, however, often employs toxic reagents and strict reaction conditions to remove trace of oxygen or moisture, and form metal halides as byproducts. The aim of the present project is to develop economical and environmentally benign synthetic methods for organoheteroatom compounds by employing addition reaction of elemental sulfur or phosphorous to unsaturated compounds.Reactions involving S-S bond cleavage of organic disulfides were investigated, and rhodium complexes were found to catalyze disulfide exchange reaction. The catalyst is also capable to exchange sulfur atoms between organic polysulfides and elemental sulfur. The results suggest that rhodium complex can be used for the activation of elemental sulfur. The method can be applied to the exchange reaction of an organic disulfide and an organic diselenide.It was also found that reaction of organic disulfide, diselenide, and 1-alkyne in the presence of rhodium complex provides the selenothiolated alkyne selectively. It is shown that the transition metal complex can discriminates sulfur and selenium atoms.A method was developed which catalyzes the addition of triphenylphosphine to ethylene, propylene, or 1-butene giving 1-alkylphosphonium salts.It is now shown that transition metal complex can effectively be used for various transformation of organosulfur and organophosphorous compounds.