Copper-mediated Trifluoromethylselenolation Of Alkyl Halides And Synthesis Of Allenyl Trifluoromethyl Thioethers

More and more applications for fluorinated molecules arebeing found in various fields. In recent years, because Trifluoromethylthio (-SCF3) has a high hydrophobicity parameter (πR= 1.44). Trifluoromethylthio (-SCF3)-substituted motifs usually possess interesting biological and physical properties and have been extensively applied in the preparation of pharmaceuticals, agrochemicals, and advanced materials.The paper consists of two parts:In part one:Numerous methods for the introduction of this group onto organic substrates are described in literature, there were considerably less efforts devoted to the development of the construction C-SeCF3 bonds. Despite their toxic nature in general, organoselenium com-pounds represent an important class of molecules which have shown useful biological and enzyme inhibitory activities. Most of these existing methods for synthesizing trifluoromethylselenolated compounds require the use of functionalized substrates, such as selenocyanates or diselenides. Given the considera-ble interest in trifluoromethyl selenide compounds, the development of new, more efficient procedures is a subject of great importance. The main job of studies in part one has two part. First, An air-stable copper(Ⅰ) trifluoromethylthiolate reagents Cu(PPh3)2SeCF3have been synthesized from Cul, Se, CF3SiMe3, and PPh3. Second, the direct introduction of a trifluoromethyseleno group at the alkyl halides was studied. The complex ligated by the bipyridine ligand proved to be a useful reagent for the nucleophilic trifluoromethylselenolation. A wide range of alkyl bromide with a number of synthetically relevant functional groups, including ether, thioether, amide, ketal, and ester may be used in this process to afford the corresponding trifluorometh-ylselenolated products in modest to excellent yields. This method represents a powerful protocol for the construction trifluoromethylselenolate compounds.In part two:the direct introduction of a trifluoromethylthio group at the allene bromide was studied. In the process, a useful reagent for the nucleophilic trifluoromethylthiolation, which is very stable to air, can react with a wide range of halides. After a series of optimization on the reaction conditions, we found that allene trifluoromethyl sulfides was accomplished in modest to excellent yields at room temperature. This reaction has the advantages of easy to operate excellent yields, ine-xpensive, environmentally friendly, and has great potential value.