3-Lithiopropyl tert-Butyl Thioether: A New γ-Functionalised Organolithium Compound (d3-Reagent) in Synthetic Organic Chemistry

Article abstract of DOI:10.1016/0040-4020(95)00749-X

The reaction of 3-bromo or 3-chloropropyl tert-butyl thioether (1a or 1'a) with and excess of lithium powder and a catalytic amount of naphthalene (2.5 mol percent) in THF at -78 deg C followed by treatment with an electrophile (H2O, D2O, Me2S2, 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 tCHO, PhCHO, Me2CO, (CH2)4CO, (CH2)5CO, PhCOMe, c-C3H5COPh> and using DTBB as the arene catalyst at 0 deg C.De-tert-butylation of products 2 with mercury(II) acetate and sulfhydric acid yields different sulfurated derivatives depending on the structure of the starting thioether.