Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

Handle URI:
http://hdl.handle.net/10754/617510
Title:
Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone
Authors:
Dehury, Niranjan; Maity, Niladri ( 0000-0002-0588-7849 ) ; Tripathy, Suman Kumar; Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Patra, Srikanta
Abstract:
Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone 2016 ACS Catalysis
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
18-Jul-2016
DOI:
10.1021/acscatal.6b01421
Type:
Article
ISSN:
2155-5435; 2155-5435
Sponsors:
This work has been supported by DST (EMR/2015/002219), New Delhi, India. ND and SKT are grateful to the University Grant Commission (UGC) and the Council of Scientific and Industrial Research (CSIR), New Delhi, India, respectively, for their fellowship. N. M. acknowledges the King Abdullah University of Science and Technology (KAUST) for the postdoctoral fellowship. The authors are grateful to the reviewers’ for their valuable comments and suggestions to improve the manuscript.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acscatal.6b01421
Appears in Collections:
Articles

Full metadata record

DC FieldValue Language
dc.contributor.authorDehury, Niranjanen
dc.contributor.authorMaity, Niladrien
dc.contributor.authorTripathy, Suman Kumaren
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorPatra, Srikantaen
dc.date.accessioned2016-07-26T09:20:37Z-
dc.date.available2016-07-26T09:20:37Z-
dc.date.issued2016-07-18-
dc.identifier.citationDinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone 2016 ACS Catalysisen
dc.identifier.issn2155-5435-
dc.identifier.issn2155-5435-
dc.identifier.doi10.1021/acscatal.6b01421-
dc.identifier.urihttp://hdl.handle.net/10754/617510-
dc.description.abstractHerein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.en
dc.description.sponsorshipThis work has been supported by DST (EMR/2015/002219), New Delhi, India. ND and SKT are grateful to the University Grant Commission (UGC) and the Council of Scientific and Industrial Research (CSIR), New Delhi, India, respectively, for their fellowship. N. M. acknowledges the King Abdullah University of Science and Technology (KAUST) for the postdoctoral fellowship. The authors are grateful to the reviewers’ for their valuable comments and suggestions to improve the manuscript.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acscatal.6b01421en
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 http://pubs.acs.org/doi/abs/10.1021/acscatal.6b01421.en
dc.titleDinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketoneen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalACS Catalysisen
dc.eprint.versionPost-printen
dc.contributor.institutionSchool of Basic Sciences, Indian Institute of Technology Bhubaneswar, Bhubaneswar, Orissa-751007, Indiaen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorMaity, Niladrien
kaust.authorBasset, Jean-Marieen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.