Ogawa Akiya, Ogawa Ikuko, Obayashi Ryoichi, Umezu Keita, Doi Mikio, Hirao Toshikazu
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
J Org Chem. 1999 Jan 8;64(1):86-92. doi: 10.1021/jo981053q.
A novel, highly selective method for introducing organic sulfur, selenium, and tellurium functions into vinylic cyclopropanes has been developed on the basis of the relative reactivities of organic dichalcogenides and chalcogen-centered radicals. Upon irradiation with the light of wavelength over 300 nm, the reaction of vinylcyclopropanes with diphenyl disulfide and diphenyl diselenide proceeds smoothly to provide the corresponding gamma-(selenoethyl)allylic sulfides regioselectively in good yields. Similarly, vinylcyclopropanes undergo regioselective thiotelluration by use of a novel (PhS)(2)-(PhTe)(2) binary system, affording the corresponding ring-opened thiotelluration product in good yields. Furthermore, the scope and limitations of this (PhS)(2)-(PhTe)(2) binary system are discussed.
基于有机二硫属化物和硫属元素中心自由基的相对反应活性，开发了一种将有机硫、硒和碲官能团引入乙烯基环丙烷的新型高选择性方法。用波长超过300nm的光照射时，乙烯基环丙烷与二苯基二硫化物和二苯基二硒化物的反应顺利进行，以良好的产率区域选择性地提供相应的γ-(硒代乙基)烯丙基硫化物。同样，乙烯基环丙烷通过使用新型的(PhS)₂-(PhTe)₂二元体系进行区域选择性硫代碲化反应，以良好的产率得到相应的开环硫代碲化产物。此外，还讨论了该(PhS)₂-(PhTe)₂二元体系的适用范围和局限性。
