Synthesis, Chromatographic Separation, Vibrational Circular Dichroism Spectroscopy, and ab Initio DFT Studies of Chiral Thiepane Tetraol Derivatives

• Published in: Journal of organic chemistry Vol. 70; no. 2; pp. 664 - 669
• Main Authors: Cerè, Vanda, Peri, Francesca, Pollicino, Salvatore, Ricci, Alfredo, Devlin, Frank J, Stephens, Philip J, Gasparrini, Francesco, Rompietti, Romina, Villani, Claudio
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 21-01-2005
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Preparations and properties; Stereoisomer; Separation; Ab initio method; Conformational analysis; Alcohol; Chiral stationary phase; Chiral compound; Chromatography; Circular dichroism; Stereoselectivity; Sulfur heterocycle; Chemical compound library; Circular dichroism spectrometry; Absolute configuration; Density functional method; Chemical synthesis
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo048629y

Optically pure enantiomers of the chiral tetrahydroxythiepane derivative 3,6-dihydroxy-4,5-O-isopropylidene-thiepane (3) are obtained using a novel protocol in which a library of all possible stereoisomers of 3 is synthesized, followed by two-step stereoselective chromatography, using, first, conventional achiral and, then, chiral stationary phases. Configurational and conformational analysis of 3 are carried out using Vibrational Circular Dichroism (VCD) spectroscopy in conjunction with ab initio DFT calculations. The absolute configuration of 3 is shown to be 3R,4S,5R,6R-(+)/3S,4R,5S,6S-(−).