Intramolecular Nucleophilic Substitution of ω-Haloalkylphosphine Derivatives.

ABSTRACT

ω-Haloalkylphosphine derivatives undergo the intramolecular nucleophilic substitution reaction upon treatment with a strong base, yielding either cycloalkylphosphine derivatives or heterocyclic phosphine derivatives. The selectivity of the cyclization of (ω-haloalkyl)alkylarylphosphine derivatives depends strongly on the distance between the electrophilic and nucleophilic carbon atoms and the structure of the phosphorus moiety. The desymmetrization of dimethylphenylphosphine sulfide followed by haloalkylation and cyclization led to the enantiomerically enriched tertiary phosphine sulfide, possessing a cyclohexyl fragment at the phosphorus.