These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: Monitoring Reaction Intermediates to Predict Enantioselectivity Using Mass Spectrometry.
    Author: Hilgers R, Yong Teng S, Briš A, Pereverzev AY, White P, Jansen JJ, Roithová J.
    Journal: Angew Chem Int Ed Engl; 2022 Sep 05; 61(36):e202205720. PubMed ID: 35561144.
    Abstract:
    Enantioselective reactions are at the core of chemical synthesis. Their development mostly relies on prior knowledge, laborious product analysis and post-rationalization by theoretical methods. Here, we introduce a simple and fast method to determine enantioselectivities based on mass spectrometry. The method is based on ion mobility separation of diastereomeric intermediates, formed from a chiral catalyst and prochiral reactants, and delayed reactant labeling experiments to link the mass spectra with the reaction kinetics in solution. The data provide rate constants along the reaction paths for the individual diastereomeric intermediates, revealing the origins of enantioselectivity. Using the derived kinetics, the enantioselectivity of the overall reaction can be predicted. Hence, this method can offer a rapid discovery and optimization of enantioselective reactions in the future. We illustrate the method for the addition of cyclopentadiene (CP) to an α,β-unsaturated aldehyde catalyzed by a diarylprolinol silyl ether.
    [Abstract] [Full Text] [Related] [New Search]