Show simple item record

dc.contributor.authorPavlovic, Ljiljana
dc.contributor.authorCarvalho de Oliveira Gomes, Bjørn
dc.contributor.authorHopmann, Kathrin Helen
dc.date.accessioned2024-10-17T10:39:37Z
dc.date.available2024-10-17T10:39:37Z
dc.date.issued2024-06-25
dc.description.abstractThe mechanistic details of the asymmetric Ni-catalyzed reductive cyclization/carboxylation of alkenes with CO2 have been revisited using DFT methods. Emphasis was put on the enantioselectivity and the mechanistic role of Lewis acid additives and in situ formed salts. Our results show that oxidative addition of the substrate is rate-limiting, with the formed Ni(II)-aryl intermediate preferring a triplet spin state. After reduction to Ni(I), enantioselective cyclization of the substrate occurs, followed by inner sphere carboxylation. Our proposed mechanism reproduces the experimentally observed enantiomeric excess and identifies critical C−H/O and C−H/N interactions that affect the selectivity. Further, our results highlight the beneficial effect of Lewis acids on CO2 insertion and suggest that in situ formed salts influence if the 5-exo or 6-endo product will be formed.en_US
dc.identifier.citationPavlovic, Carvalho de Oliveira Gomes, Hopmann. Revisiting the mechanism of asymmetric Ni-catalyzed reductive carbo-carboxylation with CO2: The additives affect the product selectivity. Chemistry - A European Journal. 2024en_US
dc.identifier.cristinIDFRIDAID 2284173
dc.identifier.doi10.1002/chem.202401631
dc.identifier.issn0947-6539
dc.identifier.issn1521-3765
dc.identifier.urihttps://hdl.handle.net/10037/35276
dc.language.isoengen_US
dc.publisherWileyen_US
dc.relation.journalChemistry - A European Journal
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2024 The Author(s)en_US
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0en_US
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)en_US
dc.titleRevisiting the mechanism of asymmetric Ni-catalyzed reductive carbo-carboxylation with CO2: The additives affect the product selectivityen_US
dc.type.versionacceptedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


File(s) in this item

Thumbnail

This item appears in the following collection(s)

Show simple item record

Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
Except where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)