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

Gellért Sipos; Arnold Ou; Brian W. Skelton; Laura Falivene; Luigi Cavallo; Reto Dorta

doi:10.1002/chem.201600378

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

Gellért Sipos, Arnold Ou, Brian W. Skelton, Laura Falivene, Luigi Cavallo, Reto Dorta

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

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.

Original language	English (US)
Pages (from-to)	6939-6946
Number of pages	8
Journal	Chemistry - A European Journal
Volume	22
Issue number	20
DOIs	https://doi.org/10.1002/chem.201600378
State	Published - Apr 10 2016

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10.1002/chem.201600378

https://repository.kaust.edu.sa/bitstream/10754/621715/1/Articlefile1.pdf

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CCDC 1433196: Experimental Crystal Structure Determination : (eta2,eta2-cycloocta-1,5-diene)-(1-(2,7-dicyclohexyl-1-naphthyl)-3-(2,7-dicyclohexyl-1-naphthyl)imidazolidin-2-yl-dene)-iridium hexafluorophosphate dichloromethane solvate
Sipos, G. (Creator), Ou, A. (Creator), Skelton, B. W. (Creator), Falivene, L. (Creator), Cavallo, L. (Creator), Dorta, R. (Creator), Sipos, G. (Creator), Ou, A. (Creator), Skelton, B. W. (Creator) & Dorta, R. (Creator), Cambridge Crystallographic Data Centre, May 14 2016
DOI: 10.5517/ccdc.csd.cc1k3c45, http://hdl.handle.net/10754/624536
Dataset
CCDC 1433194: Experimental Crystal Structure Determination : (1-(2-cyclohexyl-1-naphthyl)-3-(2-cyclohexyl-1-naphthyl)imidazolidin-2-ylidene)-(eta2,eta2-cycloocta-1,5-diene)-iridium hexafluorophosphate
Sipos, G. (Creator), Ou, A. (Creator), Skelton, B. W. (Creator), Falivene, L. (Creator), Cavallo, L. (Creator), Dorta, R. (Creator), Sipos, G. (Creator), Ou, A. (Creator), Skelton, B. W. (Creator) & Dorta, R. (Creator), Cambridge Crystallographic Data Centre, May 14 2016
DOI: 10.5517/ccdc.csd.cc1k3c23, http://hdl.handle.net/10754/624534
Dataset
CCDC 1433190: Experimental Crystal Structure Determination : (1,3-bis(2-cyclohexyl-1-naphthyl)imidazolidin-2-ylidene)-chloro-(eta2,eta2-cycloocta-1,5-diene)-iridium unknown solvate
Sipos, G. (Creator), Ou, A. (Creator), Skelton, B. W. (Creator), Falivene, L. (Creator), Cavallo, L. (Creator), Dorta, R. (Creator), Sipos, G. (Creator), Ou, A. (Creator), Skelton, B. W. (Creator) & Dorta, R. (Creator), Cambridge Crystallographic Data Centre, May 14 2016
DOI: 10.5517/ccdc.csd.cc1k3byy, http://hdl.handle.net/10754/624530
Dataset

Cite this

@article{7c04bf788fde4ad3b119432603d2935d,

title = "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. {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

author = "Gell{\'e}rt Sipos and Arnold Ou and Skelton, {Brian W.} and Laura Falivene and Luigi Cavallo and Reto Dorta",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.",

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doi = "10.1002/chem.201600378",

language = "English (US)",

volume = "22",

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publisher = "Wiley",

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T1 - Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

AU - Sipos, Gellért

AU - Ou, Arnold

AU - Skelton, Brian W.

AU - Falivene, Laura

AU - Cavallo, Luigi

AU - Dorta, Reto

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.

PY - 2016/4/10

Y1 - 2016/4/10

N2 - 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.

AB - 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.

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U2 - 10.1002/chem.201600378

DO - 10.1002/chem.201600378

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JF - Chemistry - A European Journal

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

Abstract

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Other files and links

CCDC 1433196: Experimental Crystal Structure Determination : (eta2,eta2-cycloocta-1,5-diene)-(1-(2,7-dicyclohexyl-1-naphthyl)-3-(2,7-dicyclohexyl-1-naphthyl)imidazolidin-2-yl-dene)-iridium hexafluorophosphate dichloromethane solvate

CCDC 1433194: Experimental Crystal Structure Determination : (1-(2-cyclohexyl-1-naphthyl)-3-(2-cyclohexyl-1-naphthyl)imidazolidin-2-ylidene)-(eta2,eta2-cycloocta-1,5-diene)-iridium hexafluorophosphate

CCDC 1433190: Experimental Crystal Structure Determination : (1,3-bis(2-cyclohexyl-1-naphthyl)imidazolidin-2-ylidene)-chloro-(eta2,eta2-cycloocta-1,5-diene)-iridium unknown solvate

Cite this