3-LITHIOPROPYL TERT-BUTYL THIOETHER - A NEW GAMMA-FUNCTIONALIZED ORGANOLITHIUM COMPOUND (D(3)-REAGENT) IN SYNTHETIC ORGANIC-CHEMISTRY

The reaction of 3-bromo or 3-chloropropyl tert-butyl thioether (1a or 1'a) with an excess of lithium powder and a catalytic amount of naphthalene (2,5 mol%) in THF at -78 degrees C followed by treatment with an electrophile (H2O, D2O, Me(2)S(2), CO2) at the same temperature leads, after hydrolysis, to the expected products 2. Alternatively the process can be carried out under Barbier-type reaction conditions [lithiation in the presence of the electrophile: Me(3)SiCl, Bu(t)CHO, PhCHO, Me(2)CO, (CH2)(4)CO, (CH2)(5)CO, PhCOMe, c-C(3)H(5)CdPh] and using DTBB as the arene catalyst at 0 degrees C. De-ren-butylation of products 2 with mercury(LI) acetate and sulfhydric acid yields different sulfurated derivatives depending on the structure of the starting thioether.