Bis(chloromethyl) Sulfone and Sulfoxide as Precursors of the Corresponding α,α′-Dianionic Synthons by a Chlorine-Lithium Exchange

Abstract

The DTBB-catalyzed lithiation of bis(chloromethyl) sulfone (1) and sulfoxide (3) in the presence of different carbonyl compounds [t-BuCHO, c-C₆H₁₁CHO, PhCHO, Me₂CO, Et₂CO, n-Pr₂CO, (CH₂)₄CO, (CH₂)₅CO, (c-C₃H₅)₂CO, PhCOMe, norbonan-2-one] in THF at -90 ºC, followed by hydrolysis with water at the same temperature led to the formation of the corresponding dihydroxy sulfones (2) or sulfoxides (4). Representative compounds of both series have been analyzed by X-ray crystallography.

Key words

dimethyl sulfone dianion - dimethyl sulfoxide dianion - DTBB-catalyzed lithiation - chloro-lithium exchange

References

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1

Carried out X-ray analyses. New address: Servicios Técnicos de Investigación, Planta Cero, Facultad de Ciencias, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain.

10

The single chlorine-lithium exchange (for instance a stoichiometric amount of Li) failed, giving a complex mixture of reaction products.

11

Under Barbier conditions not many electrophiles are compatible with the strongly reducing reaction mixture carbonyl compounds being appropriate for that purpose.