Synthesis and Structure of Cyclopropano-Annelated Homosesquinorbornene Derivatives Containing Pyramidalized Double Bonds: Evidence for the Sterical Effect of a Cyclopropyl Group on the Degree of CC Double-Bond Pyramidalization

endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters
have been synthesized, and their Diels−Alder cycloaddition reactions with maleic anhydride,
dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of
four adducts indicated the pyramidalization of the central double bond. Density functional theory
calculations on the isolated products and model compounds showed excellent agreement between
the experimental and theoretical determined butterfly angles. Furthermore, it has been shown
that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the
pyramidalization which is attributed to the steric interactions between the cyclopropyl group and
ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their
X-ray analysis could not be carried out. DFT calculations on model compounds showed increased
bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester.