Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

Handle URI:
http://hdl.handle.net/10754/627314
Title:
Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation
Authors:
Pluta, Roman; Krach, Patricia E.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Falivene, Laura ( 0000-0003-1509-6191 ) ; Rueping, Magnus ( 0000-0003-4580-5227 )
Abstract:
A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)
Citation:
Pluta R, Krach PE, Cavallo L, Falivene L, Rueping M (2018) Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation. ACS Catalysis 8: 2582–2588. Available: http://dx.doi.org/10.1021/acscatal.7b03118.
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
9-Feb-2018
DOI:
10.1021/acscatal.7b03118
Type:
Article
ISSN:
2155-5435; 2155-5435
Sponsors:
P.E.K. thanks the Deutsche Bundesstiftung Umwelt for financial support. We also thank Steven Terhorst and Johannes Baues for technical assistance. L.C. thanks the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Supercomputing Laboratory (KSL) at KAUST.
Additional Links:
https://pubs.acs.org/doi/10.1021/acscatal.7b03118
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPluta, Romanen
dc.contributor.authorKrach, Patricia E.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorRueping, Magnusen
dc.date.accessioned2018-03-15T09:10:57Z-
dc.date.available2018-03-15T09:10:57Z-
dc.date.issued2018-02-09en
dc.identifier.citationPluta R, Krach PE, Cavallo L, Falivene L, Rueping M (2018) Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation. ACS Catalysis 8: 2582–2588. Available: http://dx.doi.org/10.1021/acscatal.7b03118.en
dc.identifier.issn2155-5435en
dc.identifier.issn2155-5435en
dc.identifier.doi10.1021/acscatal.7b03118en
dc.identifier.urihttp://hdl.handle.net/10754/627314-
dc.description.abstractA chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.en
dc.description.sponsorshipP.E.K. thanks the Deutsche Bundesstiftung Umwelt for financial support. We also thank Steven Terhorst and Johannes Baues for technical assistance. L.C. thanks the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Supercomputing Laboratory (KSL) at KAUST.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acscatal.7b03118en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acscatal.7b03118.en
dc.subjectDFT studyen
dc.subjectfluorineen
dc.subjecthypervalent compoundsen
dc.subjectreaction mechanismen
dc.subjecttransition stateen
dc.titleMetal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computationen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalACS Catalysisen
dc.eprint.versionPost-printen
dc.contributor.institutionInstitute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germanyen
kaust.authorCavallo, Luigien
kaust.authorFalivene, Lauraen
kaust.authorRueping, Magnusen
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