Structural mapping of an unsymmetrical chemically modified cyclodextrin by high-field nuclear magnetic resonance spectroscopy

Catriona M. Spencer*, J. Fraser Stoddart, Ryszard Zarzycki

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

55 Scopus citations

Abstract

Samples of 2,6-per-O-methyl-β-cyclodextrin (DMβCD), prepared according to literature procedures, have been shown to be less than 70% pure. The major impurity has been identified as the unsymmetrical over-methylated cyclodextrin derivative (DM+1)βCD. Samples of pure DMβCD and (DM+1)βCD have been prepared by (i) benzoylating a chromatographically homogeneous mixture obtained after methylating βCD with dimethyl sulphate, (ii) separating chromatographically the resulting DMβCD heptabenzoate (DMβCD-B7) and (DM+1)βCD hexabenzoate [(DM+1 )βCD-B6], and then (iii) subjecting the pure perbenzoates to de-O-benzoylation. Both DMβCD-B7 and (DM+1)βCD-B 6 have been fully characterised. High-resolution 1H and 13C n.m.r. spectroscopy, with use of modern pulse techniques (homonuclear double resonance difference spectroscopy, COSY, J-resolved, JMOD, XHCORRD, and CHORTLE) for signal assignment and n.O.e. difference spectroscopy for residue sequencing, has been used to assign individually (i) 41 out of the 49 heterotopic protons and (ii) 29 out of the 42 heterotopic carbon atoms of the unsymmetrical (DM+1)βCD-B6 (nuclei associated with O-methyl and O-benzoyl groups were excluded from consideration). The complete spectroscopic characterisation of unsymmetrical chemically modified cyclodextrins is important in the investigation of these compounds as potential enzyme models. The necessity of preparing pure chemically modified cyclodextrin derivatives cannot be over-emphasised.

Original languageEnglish (US)
Pages (from-to)1323-1336
Number of pages14
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number9
DOIs
StatePublished - 1987

ASJC Scopus subject areas

  • Chemistry(all)

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