Many achiral molecules can be made chiral by appropriate positioning of an isotope. Accurate detection of this type of chirality has remained elusive, and there is as yet no general method for detection of isotopically chiral species. Here, we present the first application of microwave three-wave mixing to isotopically chiral molecules, detecting enantiomeric excess in ( R/ S)-benzyl-α-D alcohol. Our method is expected to be applicable to a broad range of isotopically chiral molecules with a prochiral parent species.
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http://dx.doi.org/10.1021/acs.jpca.9b02115 | DOI Listing |
Anal Chim Acta
February 2025
Institute of Physical and Analytical Chemistry, School of Exact and Natural Sciences, Tbilisi State University, 0179, Tbilisi, Georgia. Electronic address:
Background: Isotopologues resulting from the labelling of molecules with deuterium have attracted interest due to the isotope effect observed in chemistry and biosciences. Isotope effect may also play out in noncovalent interactions and mechanisms leading to intermolecular recognition. In chromatography, differences in retention time between isotopologues, as well as between isotopomers have been observed resulting in two different elution sequences (isotope effects): the normal isotope effect when heavier isotopologues retain longer than lighter analogues, and the inverse isotope effect featuring the opposite elution order.
View Article and Find Full Text PDFInt J Biol Macromol
January 2025
Key Laboratory of Organosilicon Chemistry and Materials Technology, Ministry of Education; College of Materials Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, Zhejiang 311121, China. Electronic address:
Keto reductases are crucial NAD(P)H-dependent enzymes used for the enantioselective synthesis of alcohols from prochiral ketones. Typically, the NADPH cofactor is regenerated through a second enzyme and/or substrate. However, photocatalytic cofactor regeneration using water as a sacrificial electron and hydrogen donor presents a promising alternative, albeit a challenging one.
View Article and Find Full Text PDFJ Org Chem
January 2025
Chemistry and Materials Program, College of Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Kohto-ku, Tokyo 135-8548, Japan.
Both enantiomers of 2-ethylquinazolin-4-ones bearing -CHO/CDO and CHO/CHO phenyl groups at the N3 position were prepared. These are isotopic atropisomeric compounds based on a remote and conformationally flexible H/D and C/C discrimination, and it was found that a CHCl solution of -CHO/CDO derivative shows a slight specific optical rotation. Furthermore, diastereomeric quinazolinone derivatives bearing a chiral carbon were prepared, and their stereochemical purities and rotational stability as well as the isotopic atropisomerism were verified by H NMR and chiral high-performance liquid chromatography (HPLC) analyses.
View Article and Find Full Text PDFCommun Chem
December 2024
Department of Chemistry, University of Zurich, Zurich, Switzerland.
Chirality plays a critical role in the biochemistry of life and often only one enantiomeric series is observed (homochirality). Only a few natural products have been obtained as racemates, e.g.
View Article and Find Full Text PDFJ Chromatogr A
January 2025
The Research Center of Chiral Drugs, Shanghai Frontiers Science Center for TCM Chemical Biology, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, PR China. Electronic address:
Biological aminothiols (BATs) typically exist in both reduced and oxidized forms, each exhibiting diverse biological activities. Monitoring the levels and ratios of the two forms is crucial for clinical diagnosis and understanding their roles in biological systems. In this study, we developed a method for simultaneous analysis of both reduced and oxidized BATs using a double derivatization approach combined with liquid chromatography-mass spectrometry (LC-MS).
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