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Circular dichroism of diglycosyl dichalcogenides in solution and solid state
Author(s) -
Kurtán Tibor,
Pescitelli Gennaro,
Salvadori Piero,
Kenéz Ágnes,
Antus Sándor,
Szilágyi László,
Illyés Tündezita,
Szabó Ildikó
Publication year - 2008
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.20458
Subject(s) - chemistry , chromophore , dihedral angle , chirality (physics) , time dependent density functional theory , circular dichroism , crystallography , diselenide , spectral line , helicity , computational chemistry , photochemistry , density functional theory , organic chemistry , molecule , physics , hydrogen bond , chiral symmetry breaking , selenium , quantum mechanics , astronomy , nambu–jona lasinio model , quark , particle physics
Solution and solid‐state CD spectra of nine peracetylated and deacetalyted diglycosyl disulfides were measured to study the relationship between the low‐energy CD transitions ( n 1 →σ* SS and n 2 →σ* SS ) and helicity of the inherently chiral disulfide chromophore as perturbed by chiral carbohydrate moieties. The solid‐state CD spectra were directly correlated with the reported X‐ray structures of Ac 4 GlcSSGlcAc 4 and Ac 4 GlcSSGalAc 4 , and the CD data revealed that all the disulfides have M helicity with C1SSC1′ dihedral angles −90° < φ < 0° both in solution and in the solid state. A TDDFT CD study was carried out on dimethyl diselenide which confirmed that the same quadrant rule is relevant between the signs of the low‐energy CD transitions and the diselenide torsional angle as formulated previously for the disulfide chromophore. The CD spectra of Ac 4 GlcSeSeGlcAc 4 measured in solution and in the solid state were correlated with its X‐ray structure and reproduced well by TDDFT CD calculations performed on its tetra‐ O ‐acetyl derivative. Chirality, 2008. © 2007 Wiley‐Liss, Inc.