Calculated chiroptical properties of some simple saccharides

A calculational model of the chiroptical properties of simple saccharides has been developed. The model corrects algorithmic deficiencies of an earlier version and updates the earlier model to bring calculated circular dichroism (CD) into correspondence with recent experimental observations. The present model also includes calculated CD in the 150–190 nm region of the spectrum.;The model correctly places the onset of s-s* transitions below 130 nm, reproduces the NaD optical rotation to within 10 deg cm2 dmol–1, and semi-quantitatively reproduces the 150–190 nm CD for the α and β-anomers of methyl pyransoides of glucose, galactose, and mannose.;To test the effect changes in the model had on earlier results of conformational analysis via optical rotation (OR), the OR f,Y -maps of α,α-trehalose, β-maltose, cellobiose, and methyl 3-O-(α-D-mannopyranosyl)-α-D-mannopyranoside were completed and found to agree with previous studies. Additionally the 150–190 nm CD were generated, and compared to available experimental spectra.;In an effort to further check the utility of the model, conformational analysis via OR of methyl 3-O-(α-L-rhamnopyranosyl)-α-L-rhamnopyranoside was also completed Comparison of our results to those obtained by recent molecular mechanics studies provide support to some of the conclusions of the molecular mechanics.