Comparative analysis of NMR spectral parameters and molecular dynamics of 1:6-anhydro-3:4-thia-2-O-tosyl-β-D-allopyranose and 1,6:3,4-dianhydro-2-O-tosyl-β-D-galactopyranose in the solid phase

• Published in: Journal of physical organic chemistry Vol. 18; no. 7; pp. 602 - 609
• Main Authors: Potrzebowski, Marek J., Kaźmierski, Sławomir, Olejniczak, Sebastian, Heliński, Jan, Ciesielski, Włodzimierz, Dőlle, Andreas
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.07.2005
• Subjects: 13C relaxation time; CH···O; CH···O, CH···S intermolecular contacts; CH···S intermolecular contacts; DFT GIAO calculations; molecular motion; rotating frame; solid-state NMR
• ISSN: 0894-3230; 1099-1395
• DOI: 10.1002/poc.906

A search of x‐ray data for 1:6‐anhydro‐3:4‐thia‐2‐O‐tosyl‐β‐D‐allopyranose (1) and 1:6,3:4‐dianhydro‐2‐O‐tosyl‐β‐D‐galactopyranose (2) revealed two CH·O intermolecular contacts for both compounds and one CH·S interaction for 1. Inspection of hydrogen bonding showed that these interactions are stronger for 2. The 13C relaxation times in the rotating frame,13C T*1ρ, measured at B1=36.7 kHz showed apparent differences in internal molecular motion on the kilohertz scale for both samples. A PASS‐2D experiment recorded at a spinning rate of 1 kHz was performed to establish the values of principal elements of chemical shift tensors 13C δii. DFT GIAO calculations of shielding parameters were carried out and the orientations of 13C δii were assigned. An attempt to correlate 13C NMR spectral parameters and molecular dynamics in the solid state with structure, internal motion and intermolecular interactions is presented. Copyright © 2005 John Wiley & Sons, Ltd. A search of X‐ray data for (a) and (b) revealed two of CH···O intermolecular contacts for both compounds and one CH···S interaction for (a).