Monosaccharides as Potential Chiral Probes for the Determination of the Absolute Configuration of Secondary Alcohols

Herein, a new method for the elucidation of the absolute configuration of chiral secondary alcohols is proposed. This method is an alternative for a widely used approach reported by Mosher and Dale and similar methods that are based on the ¹H NMR shift (δ) changes of protons that are attached to the substituents of the oxymethine carbon atom. The presented method is not based on tracking the chemical shift changes and utilizes stereochemically defined monosaccharides as chiral probes. A secondary alcohol is glycosylated, and the resulting glycoside is subjected to NMR studies. The observation of dipolar couplings between the protons of the monosaccharide moiety and the protons of the secondary alcohol moiety via the NOESY/ROESY spectra enables the determination of the absolute configuration of the oxymethine carbon atom

Data from: Intramolecular transformation of an antifungal antibiotic nystatin A1 into its isomer, iso-nystatin A1. Structural and molecular modeling studies

Nystatin A₁, a polyene macrolide antifungal antibiotic, in a slightly basic or acidic solution undergoes an intramolecular transformation, yielding a structural isomer, the translactonisation product, <i>iso</i>-nystatin A₁ with lactone ring diminished by two carbon atoms. Structural evidence is provided by advanced NMR and MS studies. Molecular dynamics simulations and quantum mechanics calculations gave the insight into the course and mechanism of the transformation and its effect on the conformation of the subject molecule.<br