Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling

Handle URI:
http://hdl.handle.net/10754/626621
Title:
Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling
Authors:
El-Sepelgy, Osama; Brzozowska, Aleksandra; Azofra, Luis Miguel; Jang, Yoon Kyung; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Rueping, Magnus ( 0000-0003-4580-5227 )
Abstract:
An iron-catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non-innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)
Citation:
El-Sepelgy O, Brzozowska A, Azofra LM, Jang YK, Cavallo L, et al. (2017) Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling. Angewandte Chemie International Edition 56: 14863–14867. Available: http://dx.doi.org/10.1002/anie.201708240.
Publisher:
Wiley-Blackwell
Journal:
Angewandte Chemie International Edition
Issue Date:
26-Sep-2017
DOI:
10.1002/anie.201708240; 10.1002/ange.201708240
Type:
Article
ISSN:
1433-7851
Sponsors:
L.M.A. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for support. Gratitude is also due to the KAUST Supercomputing Laboratory for providing the computational resources (use of the supercomputer Shaheen II).
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/anie.201708240/full
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.authorEl-Sepelgy, Osamaen
dc.contributor.authorBrzozowska, Aleksandraen
dc.contributor.authorAzofra, Luis Miguelen
dc.contributor.authorJang, Yoon Kyungen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorRueping, Magnusen
dc.date.accessioned2018-01-01T12:19:03Z-
dc.date.available2018-01-01T12:19:03Z-
dc.date.issued2017-09-26en
dc.identifier.citationEl-Sepelgy O, Brzozowska A, Azofra LM, Jang YK, Cavallo L, et al. (2017) Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling. Angewandte Chemie International Edition 56: 14863–14867. Available: http://dx.doi.org/10.1002/anie.201708240.en
dc.identifier.issn1433-7851en
dc.identifier.doi10.1002/anie.201708240en
dc.identifier.doi10.1002/ange.201708240en
dc.identifier.urihttp://hdl.handle.net/10754/626621-
dc.description.abstractAn iron-catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non-innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran.en
dc.description.sponsorshipL.M.A. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for support. Gratitude is also due to the KAUST Supercomputing Laboratory for providing the computational resources (use of the supercomputer Shaheen II).en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/anie.201708240/fullen
dc.rightsThis is the peer reviewed version of the following article: Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling, which has been published in final form at http://doi.org/10.1002/anie.201708240. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.en
dc.subjectcarboetherificationen
dc.subjectenol ethersen
dc.subjectheterocyclesen
dc.subjectiron catalysisen
dc.subjectsynthetic methodsen
dc.titleExperimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttlingen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalAngewandte Chemie International Editionen
dc.eprint.versionPost-printen
dc.contributor.institutionInstitute of Organic Chemistry; RWTH Aachen University; Landoltweg 1 52074 Aachen Germanyen
kaust.authorAzofra, Luis Miguelen
kaust.authorCavallo, Luigien
kaust.authorRueping, Magnusen
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