Toward calix[2]-type macrocycles: Synthesis and structural analysis of cyclic tetraketone and highly strained furanophane

Abstract

Recent progress in the synthesis of calix[3]pyrrole has proven that cyclic polyketones composed of 3,3-dialkylated pentane-2,4-diones as the repeating unit are promising precursors for strained calix-type macrocycles. Toward the synthesis of calix[2]pyrrole and calix[2]furan, which are the most strained congeners among the possible calix[[Formula: see text]]pyrroles and calix[[Formula: see text]]furans, we report the synthesis of a cyclic dimer of 3,3-dimethylpentane-2,4-dione and its furanophane derivative. These compounds were produced from a linear tetraketone precursor. Single crystal X-ray diffraction analysis revealed that the furan ring in the furanophane was highly strained with deformation angles [Formula: see text] and [Formula: see text] of 3.69[Formula: see text] and 16.00[Formula: see text], respectively. These deformation angles were the largest in the series of 1,4-diketone-linked oligofuran macrocycles. Although these two macrocyclic compounds are likely the most promising precursors for calix[2]-type macrocycles, Paal–Knorr-type pyrrole or furan ring formation did not proceed under standard conditions used for calix[3]pyrrole or calix[3]furan. Theoretical calculations indicated that the second aromatic ring formation on the cyclic tetraketone is a highly uphill process whose activation energy cannot be overcome by standard thermal reactions.