Computational Study of the Ir-Catalyzed Formation of Allyl Carbamates from CO 2 .

Autor: Gahlawat S; Department of Chemistry, UiT The Arctic University of Norway, N-9017 Tromsø, Norway.; Hylleraas Centre for Quantum Molecular Sciences, UiT The Arctic University of Norway, N-9017 Tromsø, Norway., Artelsmair M; Isotope Chemistry, Early Chemical Development, Pharmaceutical Sciences, R&D, AstraZeneca Gothenburg, SE-431 83 Mölndal, Sweden., Castro AC; Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo, Norway., Norrby PO; Data Science and Modelling, Pharmaceutical Sciences, R&D, AstraZeneca Gothenburg, SE-431 83 Mölndal, Sweden., Hopmann KH; Department of Chemistry, UiT The Arctic University of Norway, N-9017 Tromsø, Norway.
Jazyk: angličtina
Zdroj: Organometallics [Organometallics] 2024 Aug 05; Vol. 43 (17), pp. 1818-1826. Date of Electronic Publication: 2024 Aug 05 (Print Publication: 2024).
DOI: 10.1021/acs.organomet.4c00177
Abstrakt: We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO 2 ). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack by the carbamate formed in situ from CO 2 and an amine. A detailed isomeric analysis shows that the rate-determining step differs for the ( R )- and ( S )-pathways. These insights are essential for understanding reactions involving enantioselective formation of allyl carbamates from CO 2 .
Competing Interests: The authors declare no competing financial interest.
(© 2024 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
Externí odkaz: