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dc.contributor.authorPavlovic, Ljiljana
dc.contributor.authorPettersen, Martin
dc.contributor.authorGevorgyan, Ashot
dc.contributor.authorVaitla, Janakiram
dc.contributor.authorBayer, Annette
dc.contributor.authorHopmann, Kathrin Helen
dc.date.accessioned2021-05-04T07:46:11Z
dc.date.available2021-05-04T07:46:11Z
dc.date.issued2020-12-18
dc.description.abstractThe asymmetric Rh‐catalyzed hydrocarboxylation of α,β‐unsaturated carbonyl compounds was originally developed by Mikami and co‐workers but gives only moderate enantiomeric excesses. In order to understand the factors controlling the enantioselectivity and to propose novel ligands for this reaction, we have used computational and experimental methods to study the Rh‐catalyzed hydrocarboxylation with different bidentate ligands. The analysis of the C−CO<sub>2</sub> bond formation transition states with DFT methods shows a preference for outer‐sphere CO<sub>2</sub> insertion, where CO<sub>2</sub> can undergo a backside or frontside reaction with the nucleophile. The two ligands that prefer a frontside reaction, StackPhos and <sup>t</sup>Bu‐BOX, display an intriguing stacking interaction between CO<sub>2</sub> and an N‐heterocyclic ring of the ligand (imidazole or oxazoline). Our experimental results support the computationally predicted low enantiomeric excesses and highlight the difficulty in developing a highly selective version of this reaction.en_US
dc.descriptionDuplikat av https://hdl.handle.net/10037/25345. 21.02.2024 NielsC
dc.identifier.citationPavlovic Lj, Pettersen MAS, Gevorgyan A, Vaitla J, Bayer A, Hopmann KH. Computational and experimental insights into asymmetric Rh‐catalyzed hydrocarboxylation with CO2. European Journal of Organic Chemistry. 2020en_US
dc.identifier.cristinIDFRIDAID 1861881
dc.identifier.doi10.1002/ejoc.202001469
dc.identifier.issn1434-193X
dc.identifier.issn1099-0690
dc.identifier.urihttps://hdl.handle.net/10037/21140
dc.language.isoengen_US
dc.publisherWileyen_US
dc.relation.journalEuropean Journal of Organic Chemistry
dc.relation.projectIDNotur/NorStore: nn4654ken_US
dc.relation.projectIDNotur/NorStore: nn9330ken_US
dc.relation.projectIDNorges forskningsråd: 300769en_US
dc.relation.projectIDNordforsk: 85378en_US
dc.relation.projectIDNorges forskningsråd: 262695en_US
dc.relation.projectIDTromsø forskningsstiftelse: TFS2016KHHen_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/FRINATEK/300769/Norway/CATCH ME IF YOU CAN: Selective CO2 conversion via chiral CO2 trapping//en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/SFF/262695/Norway/Hylleraas Centre for Quantum Molecular Sciences//en_US
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2020 The Author(s)en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleComputational and experimental insights into asymmetric Rh‐catalyzed hydrocarboxylation with CO2en_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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