Naslov
Prediction of enantioselectivity by monitoring reaction intermediates

Autori
Hilgers, Roelant ; Teng, Sin Yong ; Briš, Anamarija ; Pereverzev, Aleksandr Y. ; White, Paul ; Jansen, Jeroen ; Roithova, Jana

Izvornik
ChemRxiv. Cambridge: Cambridge Open Engage (0000-0000) 2022 (2022); 1-16

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Diastereoisomers ; Enantioselective reactions ; Mass spectrometry ; Reaction intermediates ; Reaction kinetics

Sažetak
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 of 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.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA