Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes
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-BlackwellJournal
Chemistry - A European JournalISSN
0947-6539PubMed ID
27059164Handle URI
http://hdl.handle.net/10754/621715Is Supplemented By
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.cc1k3byyDOI:10.5517/ccdc.csd.cc1k3byy
HANDLE:http://hdl.handle.net/10754/624530
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:http://hdl.handle.net/10754/624531
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:http://hdl.handle.net/10754/624532
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:http://hdl.handle.net/10754/624533
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:http://hdl.handle.net/10754/624534
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:http://hdl.handle.net/10754/624535
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:http://hdl.handle.net/10754/624536