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>STUDIES IN STEREOCHEMISTRY. PART I: SYNTHESIS, RESOLUTION AND ABSOLUTE CONFIGURATION OF (E)-2,4-DIMETHYL-2-HEXENOIC ACID. PART II: THE DETERMINATION OF THE HEAT OF HYDROGENATION AND REARRANGEMENT BEHAVIOR OF 1,1'-SPIROBIINDENE. PART III: SYNTHESIS AND CHIROPTICAL PROPERTIES OF 5,7-DIOXOBICYCLO(2.2.2)OCT-2-ENE AND BICYCLO(2.2.2)OCTAN-2,5-DIONE.
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STUDIES IN STEREOCHEMISTRY. PART I: SYNTHESIS, RESOLUTION AND ABSOLUTE CONFIGURATION OF (E)-2,4-DIMETHYL-2-HEXENOIC ACID. PART II: THE DETERMINATION OF THE HEAT OF HYDROGENATION AND REARRANGEMENT BEHAVIOR OF 1,1'-SPIROBIINDENE. PART III: SYNTHESIS AND CHIROPTICAL PROPERTIES OF 5,7-DIOXOBICYCLO(2.2.2)OCT-2-ENE AND BICYCLO(2.2.2)OCTAN-2,5-DIONE.
Part I details the uncomplicated, high yield (80% overall) synthesis, resolution and determination of the absolute configuration of (E)-2,4-dimethyl-2-hexenoic acid, a constituent of the swarming pheromone secreted by male carpenter ants.; Part II reports the determination of the heat of hydrogenation and rearrangement behavior of spirobiindene. This compound has been reported to exhibit spiroconjugation. The heat of hydrogenation, however, indicates a large destabilization on the order of 13.7 kcal/mole, contradicting the prediction of spiroconjugative stabilization. The thermal, photochemical and alkali metal catalyzed rearrangement of this compound gave 3,4-benzofluorene as the only observed product, indicating that the alkenyl group migrates to the total exclusion of the aryl group. The photochemical and alkali metal induced reactions were essentially quantitative. Acid catalyzed rearrangement of spirobiindene was not observed.; Part III details the synthesis, resolution and determination of chiroptical properties of bicyclo(2.2.2)octa-2,5-dione and 2,5-dioxo-bicyclo(2.2.2)oct-7-ene. The homoconjugated dione had an optical rotatory dispersion molecular amplitude of 90,400 degrees and circular dichroism molecular ellipticity of 55,800 degrees. The specific rotation at the sodium D line was found to be -1030 (c = 0.036 in cyclohexane). The saturated dione was found to have an ORD molecular amplitude of -3370 degrees, a CD molecular ellipticity of -2581 degrees and a specific rotation at the sodium D line of -40.7 (c = 0.45 in cyclohexane). The absolute configuration of the homoconjugated dione was determined by application of the generalized octant rule and supported by application of the restricted octant rule to the saturated dione.
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