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Oxidation and [beta]-Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N-Heterocyclic Carbene Ligands

Chemistry : a European journal, 2015-12, Vol.21 (49), p.17877 [Peer Reviewed Journal]

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ;ISSN: 0947-6539 ;EISSN: 1521-3765 ;DOI: 10.1002/chem.201502910 ;CODEN: CEUJED

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  • Title:
    Oxidation and [beta]-Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N-Heterocyclic Carbene Ligands
  • Author: Jimenez, M Victoria ; Fernandez-Tornos, Javier ; Modrego, F Javier ; Perez-Torrente, Jesús J ; Oro, Luis A
  • Subjects: Oxidation
  • Is Part Of: Chemistry : a European journal, 2015-12, Vol.21 (49), p.17877
  • Description: The borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for CC bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)-cyclooctadiene complexes having a NHC ligand with a O- or N-functionalised wingtip efficiently catalysed the oxidation and [beta]-alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex [Ir(NCCH3)(cod)(MeIm(2- methoxybenzyl))][BF4] (cod=1,5-cyclooctadiene, MeIm=1-methylimidazolyl) having a rigid O-functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF0) of 1283h-1, and also in the [beta]-alkylation of 2-propanol with butan-1-ol, which gives a conversion of 94% in 10h with a selectivity of 99% for heptan-2-ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross-aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new CC bond that involves the reaction of an O-bound enolate generated in the basic medium with the electrophilic aldehyde.
  • Publisher: Weinheim: Wiley Subscription Services, Inc
  • Language: English
  • Identifier: ISSN: 0947-6539
    EISSN: 1521-3765
    DOI: 10.1002/chem.201502910
    CODEN: CEUJED
  • Source: Alma/SFX Local Collection
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