Polychlorinated materials as a source of polyanionic synthons

The reaction of dichloromethane (1a) or dichlorodideuteriomethane (1b) with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol %) in the presence of a carbonyl compound 2 (1:2 molar ratio) in THF at -40 degrees C yields, after hydrolysis, the corresponding 1,3-diols 3 in moderate yields. The process is applied to other gem-dichlorinated materials such as 7,7-dichloro[4.1.0]heptane (4), 1,1-dichlorotetramethylcyclopropane (7) and dichloromethyl methyl ether (10), using pivalaldehyde as electrophile. Starting from 1,1,1-trichlorinated compounds or tetrachloromethane (14) and using chlorotrimethylsilane as electrophile at temperatures ranging between -80 and -90 degrees C, the corresponding polysilylated compounds 15-17 are prepared applying the mentioned methodology.