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

有机二硫属化合物与碳-碳不饱和化合物之间的自由基反应已被精确地研究。基于有机二硫属化合物和硫属中心自由基的相对反应性，已经变得明显的是，两个不同的硫属基团可以同时引入到各种碳-碳多重键中，具有优异的选择性。在波长大于300 nm的光照射下，乙炔与有机二硫化物和二硒化物的反应平稳地发生，区域选择性地提供相应的硫代硒化产物。类似的加成反应可用于联烯和1，3-二烯，分别以良好的产率得到β-硒代烯丙基硫化物和γ-（硒甲基）-烯丙基硫化物。对于乙烯基环丙烷，通过环丙烷的开环发生硫硒化，得到γ-（硒甲基）烯丙基硫化物。与烯炔，硫硒化通过自由基环化被成功地证明。此外， ...更多信息 本发明涉及有机二硫属化物的新型混合体系，即，已经开发了二硫化物-二碲化物混合体系和二硒化物-二碲化物混合体系。这两种体系都需要用波长超过400 nm的光照射，因为UV或近UV光会导致带有光敏C-Te键的产物分解。从乙炔分别得到β-硫代和β-硒代乙烯基碲化物。然而，对于联二烯和1，3-二烯，根本没有形成所需的硫代碲化产物，而是获得了二硫代化产物。通过对二硫醚-二碲化物-联烯体系的进一步研究，成功地发展了一种新的碲化物催化联烯与二硫醚的二硫羟化反应。类似地，公开了硒化物催化的1，3-二烯的二硫醚化，得到1，4-二硫醚化产物。这两种体系都能有效地进行联烯和1，3-二烯的二硫化反应，而这在使用二硫化物单一体系时是很难实现的。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