Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

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Type
Article
Authors
Sipos, Gellért
Ou, Arnold
Skelton, Brian W.
Falivene, Laura cc
Cavallo, Luigi cc
Dorta, Reto
KAUST Department
Chemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2016-04-10
Online Publication Date
2016-04-05
Print Publication Date
2016-05-10
Embargo End Date
2017-04-10
Permanent link to this record
http://hdl.handle.net/10754/621715

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Abstract
N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Citation
Sipos G, Ou A, Skelton BW, Falivene L, Cavallo L, et al. (2016) Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes. Chem Eur J 22: 6939–6946. Available: http://dx.doi.org/10.1002/chem.201600378.
Sponsors
G.S. thanks the UWA for an International Postgraduate Research Scholarship. R.D. thanks the Australian Research Council for generous funding (FT130101713). The Centre for Microscopy, Characterisation & Analysis at the UWA is thanked for providing facilities and assistance. L. C. thanks the King Abdullah University of Science and Technology for financial support.
Publisher
Wiley
Journal
Chemistry - A European Journal
DOI
10.1002/chem.201600378
PubMed ID
27059164
Additional Links
https://api.research-repository.uwa.edu.au/files/38275922/Sipos_et_al_2016Unusual_NHC_Iridium_I_.pdf
Relations
Is Supplemented By:
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433190: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3byy. DOI: 10.5517/ccdc.csd.cc1k3byy HANDLE: 10754/624530
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433191: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3bzz. DOI: 10.5517/ccdc.csd.cc1k3bzz HANDLE: 10754/624531
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433192: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3c01. DOI: 10.5517/ccdc.csd.cc1k3c01 HANDLE: 10754/624532
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433193: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3c12. DOI: 10.5517/ccdc.csd.cc1k3c12 HANDLE: 10754/624533
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433194: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3c23. DOI: 10.5517/ccdc.csd.cc1k3c23 HANDLE: 10754/624534
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433195: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3c34. DOI: 10.5517/ccdc.csd.cc1k3c34 HANDLE: 10754/624535
  • [Dataset]
    Sipos, G., Ou, A., Skelton, B. W., Falivene, L., Cavallo, L., & Dorta, R. (2016). CCDC 1433196: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k3c45. DOI: 10.5517/ccdc.csd.cc1k3c45 HANDLE: 10754/624536
Collections
Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)