Asymmetric hydrogenation of ketones using Ir(III) complexes of N-alkyl-N’-tosyl-1,2-ethanediamine ligands

Martins, José Eduardo Damas; Morris, David J.; Wills, Martin

doi:10.1016/j.tetlet.2008.11.101

Cited by 35 publications

(22 citation statements)

References 69 publications

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“…In previous studies, 15 we had examined only the tosylated derivatives of DPEN 1. In order to understand the importance of the structure of the sulfonamide part, a series of sulfonamides were selected for further studies.…”

Section: Resultsmentioning

confidence: 99%

“…The incorporation of a N'-propyl group was selected as this had given the highest selectivity when used in the tosylated catalyst series. 15 In each case the (S,S) enantiomers of diamines were prepared.…”

Section: Phmentioning

confidence: 99%

“…15 The results are summarized in Table 1. 2-Methylacetophenone was selected for study because it had given particularly promising results in preliminary results, and because orthosubstituted substrates can be challenging substrates to reduce in high ee.…”

Section: Phmentioning

confidence: 99%

“…2-Methylacetophenone was selected for study because it had given particularly promising results in preliminary results, and because orthosubstituted substrates can be challenging substrates to reduce in high ee. Of the ligands tested, the best results were obtained using those with relatively unhindered aromatic rings containing electron withdrawing groups (entries 3,4,6,12,13,15). With the exception of ligand 9l, diamines containing substituents at the ortho-position(s) gave lower asymmetric inductions (entries 7-9), and those with two ortho-substituents were particularly poor, possibly for steric reasons.…”

Section: Phmentioning

confidence: 99%

“…7,8 In recently reported preliminary studies, we reported that N'-alkylated derivatives of TsDPEN 3 can be combined with IrCl 3 to form a competent catalyst for the reduction of acetophenone derivatives in ees of up to 84% (Scheme 1). 15 Although the activity of these catalysts is lower than that of phosphine-derived catalysts, their ease of preparation from stable materials and a simple Ir(III) complex makes them attractive as a simple system for the reduction of selected ketones. The use of iridium was also shown to be important; ruthenium or rhodium complexes formed catalysts which also reduced the arene ring of the substrate.…”

Section: Introductionmentioning

confidence: 99%

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Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

Martins

Wills

2009

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Section: Resultsmentioning

confidence: 99%

Section: Phmentioning

confidence: 99%

Section: Phmentioning

confidence: 99%

Section: Phmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

Martins

Wills

2009

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Application of Tethered Ruthenium Catalysts to Asymmetric Hydrogenation of Ketones, and the Selective Hydrogenation of Aldehydes

et al. 2012

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, 1974-and Wills, Martin. (2012 Application of tethered ruthenium catalysts to asymmetric hydrogenation of ketones, and the selective Hydrogenation of aldehydes. Advanced Synthesis & Catalysis, 354 (13). pp. 2545-2555. Permanent WRAP url:http://wrap.warwick.ac.uk/55017 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available. Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Abstract. An improved method for the synthesis of tethered ruthenium(II) complexes of monosulfonylated diamines is described, together with their application to hydrogenation of ketones and aldehydes. The complexes were applied directly, in their chloride form, to asymmetric ketone hydrogenation, to give products in excess of 99% ee in the best cases, using 30 bar of hydrogen at 60 °C , and to the selective reduction of aldehydes over other functional groups.

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Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp³‐C−H Noncovalent Interactions

et al. 2020

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Iridium-catalyzed enantioselective transfer hydrogenation of ketones with formic acid was developed using a prolinol-phosphine chiral ligand. Cooperative action of the iridium atom and the ligand through alcohol-alkoxide interconversion is crucial to facilitate the transfer hydrogenation. Various ketones including alkyl aryl ketones, ketoesters, and an aryl heteroaryl ketone were competent substrates. An attractive feature of this catalysis is efficient discrimination between the alkyl and aryl substituents of the ketones, promoting hydrogenation with the identical sense of enantioselection regardless of steric demand of the alkyl substituent and thus resulting in a rare case of highly enantioselective transfer hydrogenation of tert-alkyl aryl ketones. Quantum chemical calculations revealed that the sp 3-CÀ H/π interaction between an sp 3-CÀ H bond of the prolinol-phosphine ligand and the aryl substituent of the ketone is crucial for the enantioselection in combination with OÀ H•••O/sp 3-CÀ H•••O two-point hydrogen-bonding between the chiral ligand and carbonyl group.

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Asymmetric hydrogenation of ketones using Ir(III) complexes of N-alkyl-N’-tosyl-1,2-ethanediamine ligands

Cited by 35 publications

References 69 publications

Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

Application of Tethered Ruthenium Catalysts to Asymmetric Hydrogenation of Ketones, and the Selective Hydrogenation of Aldehydes

Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp³‐C−H Noncovalent Interactions

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Asymmetric hydrogenation of ketones using Ir(III) complexes of N-alkyl-N’-tosyl-1,2-ethanediamine ligands

Cited by 35 publications

References 69 publications

Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

Application of Tethered Ruthenium Catalysts to Asymmetric Hydrogenation of Ketones, and the Selective Hydrogenation of Aldehydes

Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp3‐C−H Noncovalent Interactions

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Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp³‐C−H Noncovalent Interactions