Highly Selective Thioselenation of Vinylcyclopropanes with a (PhS)₂−(PhSe)₂ Binary System and Its Application to Thiotelluration

Abstract

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.

SELENBP1 expression in the prefrontal cortex of subjects with schizophrenia

“…Although the exact function of SELENBP1 has yet to be characterised, it is known to bind Se, 44 , 45 a trace element involved in neuroprotection. 46 , 47 , 48 , 49 , 50 , 51 It is of note that Se deficiency has been associated with higher rates of schizophrenia 52 , 53 and some studies have shown lower plasma Se concentrations in patients with schizophrenia, 54 , 55 whereas others showed that Se is unchanged in the blood and serum of patients. 56 , 57 Thus, it would be beneficial to determine the Se concentrations in CNS regions in subjects with schizophrenia to ascertain whether there is a link between Se levels and SELENBP1 expression.…”

Highly Selective Perfluoroalkylation of Unsaturated Molecules upon Photoirradiation in BTF as an Organic/Fluorous Hybrid Solvent

“…Unique reactions based on the different characteristic features of disulfides and diselenides in radical reactions have already been reported, such as the thioselenation of alkynes [58], alkenes [59,60], allenes [61], enynes [58], and vinylcyclopropanes [62]. These reactions clearly demonstrate the efficacy of mixed heteroatom systems for the highly selective introduction of two (or more) heteroatom functional groups into organic molecules [55,[63][64][65].…”

Stereoselective synthesis of vinylic (Z)-vic-bis(arylchalcogenides)

“…The products are formed exclusively or preferentially with the E-configuration [4]. The thiotelluration and selenotelluration of acetylenes was also described for terminal alkynes, although less efficiently [5].…”