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  • Carbolithiation for the generation of cyclooctadienyl anions and tandem electrocyclization/alkylation to functionalized cis-bicyclo[3.3.0]octenes.

Carbolithiation for the generation of cyclooctadienyl anions and tandem electrocyclization/alkylation to functionalized cis-bicyclo[3.3.0]octenes.

Journal of the American Chemical Society (2004-03-18)
David R Williams, Jonathan T Reeves
ABSTRACT

A powerful cascade reaction process for the construction of functionalized cis-bicyclo[3.3.0]octenes has been developed. Carbolithiation of 3-methylene-1,4-cyclooctadiene with 1 degrees , 2 degrees , or 3 degrees alkyllithium reagents leads to cyclooctadienyl anions, which undergo disrotatory electrocyclization and subsequent trapping with carbon, oxygen, sulfur, or silicon electrophiles to provide functionalized cis-bicyclo[3.3.0]octenes. Transmetalation of the allyllithium intermediates allowed access to the cuprate manifold of reactivity. The rapid construction of a linear triquinane using this methodology demonstrates the potential for synthetic applications.