A series of enantiomers of cyclic and linear dipeptides containing aromatic amino acids was prepared and chromatographed on beta- and gamma-cyclodextrin (CD) columns. The retention times, separation factor alpha and resolution values were calculated. The relevance of the distance of the chiral center from the phenyl ring for chiral resolution was studied. A model was developed using X-ray crystallographic data for an inclusion complex of beta-CD and the enantiomers of cyclic (Phe-Gly).
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http://dx.doi.org/10.1016/s0021-9673(01)95782-6 | DOI Listing |
Org Lett
March 2025
Friedrich Schiller University Jena, Institute for Organic Chemistry and Macromol. Chemistry, Humboldtstr. 10, D-07743 Jena, Germany.
The total synthesis of -derived cyclic lipodepsipeptide anikasin was achieved. Using a depsipeptide building block and balanced protecting groups on the branching d--Thr residue, the synthesis was established semiautomatically on a synthesizer. Buffered deprotections minimized side reactions and afforded synthetic anikasin and its enantiomer.
View Article and Find Full Text PDFChirality
February 2025
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Moscow, Russian Federation.
An enantioselective voltammetric sensor (EVS) comprising a paste electrode made of graphitized thermal Carboblack C (CBPE) modified with a Ni(II) complex based on (S)-(2-aminomethyl)pyrrolidine and 3,5-di-tert-butylsalicylaldehyde was developed for the recognition and determination of naproxen (Nap) enantiomers. The proposed sensor was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS-SEM), Fourier-transform infrared spectroscopy (FT-IR), molecular dynamics and quantum chemical simulations, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) methods. Using the differential pulse voltammetry (DPV), the CBPE@(S)-Ni sensor was found to have good selectivity for Nap enantiomers (i/i = 1.
View Article and Find Full Text PDFChemistry
March 2025
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
Unprecedented (2E,4E,6Z,8Z)-nona-2,4,6,8-tetraenoate derivatives highly substituted by aryl groups have been synthesized by the reaction of rhodium complexes having aryl-substituted hexa-1,3,5-trienyl ligands with acrylates. These compounds have potential axial chirality, and their enantiomers are isolable by the chiral HPLC technique. Although the racemization barrier of isolated enantiomers was not high, it was found that a cyclic dimer synthesized by head-to-tail transesterification of a modified analog has quite a stable axial chirality even at a high temperature.
View Article and Find Full Text PDFEnantiospecific state transfer of chiral molecules is extremely important because enantiomers coexist in many biologically active compounds and play significantly different physiological, pharmacological, and biological roles. The inherently strong electric-dipole optical approaches based on the cyclic three-level model of chiral molecules have been extensively discussed. But, for the cases of large chiral molecules and/or chiral molecules of low asymmetry, the four-level model with two sub-loops is more realistic to describe the molecules.
View Article and Find Full Text PDFBeilstein J Org Chem
October 2024
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Carbon capture and utilisation (CCU) technologies offer a compelling strategy to mitigate rising atmospheric carbon dioxide levels. Despite extensive research on the CO insertion into epoxides to form cyclic carbonates, the stereochemical implications of this reaction have been largely overlooked, despite the prevalence of racemic epoxide solutions. This study introduces an in silico approach to design asymmetric frustrated Lewis pairs (FLPs) aimed at controlling reaction stereochemistry.
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