116084-52-7Relevant academic research and scientific papers
FACILE CONSTRUCTION OF TERPENOID FRAMEWORKS BY CYCLOADDITIONS WITH METHYL 2-CHLOROCYCLOPROYLIDENACETATE
Spitzner, Dietrich,Engler, Anita,Wagner, Peter,Meijere, Armin De,Bengtson, Gisela,et al.
, p. 3213 - 3224 (1987)
Methyl 2-chlorocyclopropylidenacetate (2-Cl) smoothly cycloadds to cyclopentadiene and 2,3-dimethylbutadiene at room temperature.With the donorsubstituted cyclohexadienes 6, 9 at elevated temperatures (60, 120 deg C respectively) 2-Cl reacts without any observable regioselectivity.In contrast, 2-Cl, when treated with lithium cyclohexadienolates 13 undergoes completely regioselective iterative Michael additions with subsequent intramolecular γ-elimination to give tricyclic γ-ketoesters 16 in good to excellent yields.The products 16 can readily be transformed to multifunctional bicyclooctane as well as bicyclooctane derivatives 17.A rationalization of the unprecedented reactovity of 2-Cl on the basis of its available structural features (IP(?), 1JC,C', C=C bond length) is offered.
