Solvent effects on the conformational distribution and optical rotation of g-methyl paraconic acids and esters

A computational investigation of the optical rotatory power of cis and trans 2-methyl-5-oxo-tetrahydro-3-furancarboxylic acids and the corresponding methyl and ethyl esters is presented. Solvent effects on both the conformational space and the rotatory power are analyzed by comparing results obtained in vacuo with those computed—using the Polarizable Continuum Model—in methanol. A comparison with experimental observations for the optical rotatory power of the title compounds in methanol is also carried out, in a few cases also for several wavelengths. Agreement between theory and experiment is in all cases excellent, in particular when solvent effects are included both in the geometry optimization and in the calculation of the OR, thus confirming the validity of the computational procedure adopted, even for this challenging family of floppy molecules. Chirality, 2006. © 2006 Wiley-Liss, Inc.