Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation

Gavin Dyson; Jean-Cedric Frison; Adrian C. Whitwood; Richard E. Douthwaite

doi:10.1039/b909290k

Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation

Gavin Dyson, Jean-Cedric Frison, Adrian C. Whitwood, Richard E. Douthwaite

Chemistry

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

Abstract

Rhodium and iridium complexes of chiral NHC-phenolimine and NHC-amine ligands have been prepared and studied for asymmetric transfer hydrogenation. X-ray and NMR spectroscopy show that for NHC-phenolimine complexes abstraction of chloride results in a change in ligand coordination from NHC only to chelating NHC-imine. Complexes of NHC-amines are inactive for transfer hydrogenation, whereas complexes of NHC-phenolimines are active at room temperature for a range of aryl containing ketones. Enantioselectivity is very sensitive to the NHC N-substituent resulting in a switch in the predominant enantiomer.

Original language	English
Pages (from-to)	7141-7151
Number of pages	11
Journal	Dalton Transactions
Volume	38
Issue number	35
DOIs	https://doi.org/10.1039/b909290k
Publication status	Published - 2009

Keywords

C-H ACTIVATION
EFFICIENT TRANSFER HYDROGENATION
KETO-ENOL EQUILIBRIA
CATALYTIC-ACTIVITY
IMIDAZOLIUM SALTS
PALLADIUM(II) COMPLEXES
COORDINATION CHEMISTRY
STRUCTURAL VARIATION
RUTHENIUM COMPLEXES
KINETIC RESOLUTION

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10.1039/b909290k

http://pubs.rsc.org/en/Content/ArticleLanding/2009/DT/b909290k

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title = "Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation",

abstract = "Rhodium and iridium complexes of chiral NHC-phenolimine and NHC-amine ligands have been prepared and studied for asymmetric transfer hydrogenation. X-ray and NMR spectroscopy show that for NHC-phenolimine complexes abstraction of chloride results in a change in ligand coordination from NHC only to chelating NHC-imine. Complexes of NHC-amines are inactive for transfer hydrogenation, whereas complexes of NHC-phenolimines are active at room temperature for a range of aryl containing ketones. Enantioselectivity is very sensitive to the NHC N-substituent resulting in a switch in the predominant enantiomer.",

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author = "Gavin Dyson and Jean-Cedric Frison and Whitwood, {Adrian C.} and Douthwaite, {Richard E.}",

year = "2009",

doi = "10.1039/b909290k",

language = "English",

volume = "38",

pages = "7141--7151",

journal = "Dalton Transactions",

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publisher = "The Royal Society of Chemistry",

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TY - JOUR

T1 - Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation

AU - Dyson, Gavin

AU - Frison, Jean-Cedric

AU - Whitwood, Adrian C.

AU - Douthwaite, Richard E.

PY - 2009

Y1 - 2009

N2 - Rhodium and iridium complexes of chiral NHC-phenolimine and NHC-amine ligands have been prepared and studied for asymmetric transfer hydrogenation. X-ray and NMR spectroscopy show that for NHC-phenolimine complexes abstraction of chloride results in a change in ligand coordination from NHC only to chelating NHC-imine. Complexes of NHC-amines are inactive for transfer hydrogenation, whereas complexes of NHC-phenolimines are active at room temperature for a range of aryl containing ketones. Enantioselectivity is very sensitive to the NHC N-substituent resulting in a switch in the predominant enantiomer.

AB - Rhodium and iridium complexes of chiral NHC-phenolimine and NHC-amine ligands have been prepared and studied for asymmetric transfer hydrogenation. X-ray and NMR spectroscopy show that for NHC-phenolimine complexes abstraction of chloride results in a change in ligand coordination from NHC only to chelating NHC-imine. Complexes of NHC-amines are inactive for transfer hydrogenation, whereas complexes of NHC-phenolimines are active at room temperature for a range of aryl containing ketones. Enantioselectivity is very sensitive to the NHC N-substituent resulting in a switch in the predominant enantiomer.

KW - C-H ACTIVATION

KW - EFFICIENT TRANSFER HYDROGENATION

KW - KETO-ENOL EQUILIBRIA

KW - CATALYTIC-ACTIVITY

KW - IMIDAZOLIUM SALTS

KW - PALLADIUM(II) COMPLEXES

KW - COORDINATION CHEMISTRY

KW - STRUCTURAL VARIATION

KW - RUTHENIUM COMPLEXES

KW - KINETIC RESOLUTION

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U2 - 10.1039/b909290k

DO - 10.1039/b909290k

M3 - Article

SN - 1477-9234

VL - 38

SP - 7141

EP - 7151

JO - Dalton Transactions

JF - Dalton Transactions

IS - 35

ER -

Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation

Abstract

Keywords

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