Computational Study of the Ir-Catalyzed Formation of Allyl Carbamates from CO2

We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO2). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack b...

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Bibliographic Details
Published in:Organometallics 2024-09, Vol.43 (17), p.1818-1826
Main Authors: Gahlawat, Sahil, Artelsmair, Markus, Castro, Abril C., Norrby, Per-Ola, Hopmann, Kathrin H.
Format: Article
Language:English
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Summary:We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO2). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack by the carbamate formed in situ from CO2 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 CO2.
ISSN:0276-7333
1520-6041
1520-6041
DOI:10.1021/acs.organomet.4c00177