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

Sahil Gahlawat; Markus Artelsmair; Abril C Castro; Per-Ola Norrby; Kathrin H Hopmann

doi:10.1021/acs.organomet.4c00177

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

Organometallics. 2024 Aug 5;43(17):1818-1826. doi: 10.1021/acs.organomet.4c00177. eCollection 2024 Sep 9.

Authors

Sahil Gahlawat^{1

2}, Markus Artelsmair³, Abril C Castro⁴, Per-Ola Norrby⁵, Kathrin H Hopmann¹

Affiliations

¹ Department of Chemistry, UiT The Arctic University of Norway, N-9017 Tromsø, Norway.
² Hylleraas Centre for Quantum Molecular Sciences, UiT The Arctic University of Norway, N-9017 Tromsø, Norway.
³ Isotope Chemistry, Early Chemical Development, Pharmaceutical Sciences, R&D, AstraZeneca Gothenburg, SE-431 83 Mölndal, Sweden.
⁴ Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo, Norway.
⁵ Data Science and Modelling, Pharmaceutical Sciences, R&D, AstraZeneca Gothenburg, SE-431 83 Mölndal, Sweden.

Abstract

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.