Organosilane‐Induced Synthesis and Functionalization of Sulfur‐Containing Compounds

摘要: Reactions of organothiosilanes with organic substrates generally lead to delivery a sulfur moiety onto the target molecule, precise outcome being related structure silyl sulfide used. Aromatic and aliphatic sulfides react carbonyl compounds under acidic or basic conditions afford thioacetals thioketals, but reactions more activated such as α,β-unsaturated acylsilanes give Michael adducts, which represent versatile intermediates in synthesis. Silyl can also participate substitution enol ethers vinyl sulfides. On contrary, hexamethyldisilathiane reacts various catalysis CoCl2·6H2O CF3SO3SiMe3 thionation unit, thereby providing general access thioketones thioaldehydes, be trapped situ by dienes. The use reaction cyclohexadiene gives rise interesting feature that stereopredetermined either endo exo isomer obtained. Furthermore, when using aromatic heteroaromatic o-azidoaldehydes, reactivity may finely tuned drive towards synthesis o-azidothioaldehydes, fused isothiazole ring systems, o-amino aldehydes thioaldehydes. Lastly, taking advantage high C−Si bond fluoride ion catalysis, selective regiospecific thiophilic functionalizations thioketones, dithioesters, trithiocarbonates, their sulfines organosilanes allylsilanes, benzylsilane, α-hetero-substituted nucleophiles realized.