A study of the stereochemistry of 2-aryl-4,5-dimethyl-1,3-dioxolanes by cholesteric induction in nematic phases and circular dichroism spectroscopy.
[Chemical reaction: See text] The circular dichroism spectra and the twisting ability of a series of 2-aryl-4,5-dimethyl-1,3-dioxolanes used as dopants in nematic solvents have been related to their absolute configuration. Whereas the circular dichroism (CD) spectra are deeply affected by the substituents present in the aromatic ring, which in several cases cause sign inversion, the helical twisting power beta is only marginally influenced. The values of beta also seem not very sensitive to the rotamer population around the aromatic ring; this indicates the predominant importance of the chiral dioxolane ring in determining the cholesteric induction. These facts can be explained by the different nature of the two observables: in CD, the chirality is read by the absorbing chromophore and is deeply influenced even by small changes of this group. In cholesteric induction we are dealing instead with chiral solute-solvent interactions that determine a twist in the solvent. In light of the present and previous results, this process seems predominantly determined by short-range interactions, which are modulated by the molecular shape. From a practical point of view, a configurational correlation using CD for the present series of compounds seems problematic, while the values of beta are nicely correlated to the absolute configurations. Calculations with the surface chirality method predict well the sign and order of magnitude of beta and their limited sensitivity to the phenyl substituents and rotamer population.
Pieraccini
Silvia
S
Alma Mater Studiorum--Università di Bologna, Dipartimento di Chimica Organica "A. Mangini", Via S. Giacomo 11, I-40126 Bologna, Italy.
Ferrarini
Alberta
A
Gottarelli
Giovanni
G
Lena
Stefano
S
Masiero
Stefano
S
Spada
Gian Piero
GP