Development of New Processes for the Introduction of Heteroatoms and their Synthetic Applications

有机二硫族化合物与碳-碳不饱和化合物之间的自由基反应进行了精确的研究。根据有机二硫族化合物和以硫为中心的自由基的相对反应活性，可以明显地看出两个不同的硫族基团可以同时引入各种碳-碳多键中，并具有优异的选择性。在波长超过300 nm的光照射下，乙炔与有机二硫化物和二硒化物的反应可以顺利进行，从而提供相应的区域选择性硫代硒化产物。类似的添加物可用于烯和1,3-二烯，分别以较高的收率得到β -硒烯丙基硫化物和γ -（硒甲基）烯丙基硫化物。对于乙烯基环丙烷，通过环丙烷开环发生硫代硒化反应，得到-（硒甲基）烯丙基硫化物。对于炔，通过自由基环化成功地证明了硫代硒化。此外，还开发了新的有机二硫族化合物混合体系，即二硫化物-二碲化物混合体系和二硒-二碲化物混合体系。这两种体系都需要波长超过400nm的光照射，因为紫外线或近紫外线会导致带有光敏C-Te键的产物分解。因此，从乙炔分别得到-硫代和-硒代碲化物。然而，对于烯和1,3-二烯，根本不会形成所需的硫代化产物，而是得到二硫代化产物。对该体系的进一步研究，成功地开发了一种新的碲催化的烯与二硫化物的二硫代化反应。类似地，公开了一种硒催化1,3-二烯的二硫化以得到1,4-二硫化产物。这两种体系都能有效地对烯和1,3-二烯进行二硫化，这是使用二硫化单一体系难以实现的。少

Radical reactions between organic dichalcogenides and carbon-carbon unsaturated compounds have been investigated precisely. Based on the relative reactivities of organic dichalcogenides and chalcogen-centered radicals, it has become apparent that two different chalcogeno-groups can be introduced simultaneously into a variety of carbon-carbon multiple bonds with excellent selectivity. Upon irradiation with the light of wavelength over 300 nm, the reaction of acetylenes with organic disulfides and diselenides takes place smoothly to provide the corresponding thioselenation products regioselectively. Similar additions can be employed with allenes and 1,3-dienes, affording beta-selenoallylic sulfieds and gamma- (selenomethyl) -allylic sulfides, respectively, in good yields. With vinylcyclopropanes, thioselenation via ring-opening of cyclopropane occurs to give gamma- (selenomethyl) allylic sulfides. With enynes, thioselenation via radical cyclization is demonstrated successfully. In additi … More on, novel mixed systems of organic dichalcogenides, i.e., a disulfide-ditelluride mixed system and a diselenide-ditelluride mixed system have been developed. Both systems require the irradiation with light of wavelength over 400nm, because UV or near UV light causes the decomposition of the products bearing a photo-sensitive C-Te bond. From acetylenes are thus obtained beta-thio-and beta-selenovinylic tellurides, respectively. With allenes and 1,3-dienes, however, the desired thiotelluration products are not formed at all, but instead dithiolation products are obtained. Further investigation on this disulfide-ditelluride-allene system leads to successful development of a novel telluride-catalyzed dithiolation reaction of allenes with disulfides. Similary, a selenide-catalyzed dithiolation of 1,3-dienes to give 1,4-dithiolation products are disclosed. Both systems has enabled the efficient dithiolation of allenes and 1,3-dienes, which is difficult to be attained by using a disulfide single system. Less