Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes
Abstract: Enantioselective C−H amination at a benzylic methylene is a vital disconnection towards chiral benzylamines. Here we disclose that butyric and valeric acid‐derived tertiary amides can undergo highly enantioselective benzylic amination using an achiral anionic Rh complex that is ion‐paired with a Cinchona alkaloid‐derived chiral cation. A broad scope of compounds can be aminated encompassing numerous arene substitutions, amides, and two different chain lengths. Excellent tolerance of ortho substituents was observed, which has not been achieved before in asymmetric intermolecular C−H amination with Rh. We speculate that the tertiary amide group of the substrate engages in hydrogen bonding interactions directly with the chiral cation, enabling a high level of organisation at the transition state for C−H amination. This is in contrast with our previous work where a substrate bearing a hydrogen bond donor was required. Control experiments led to the discovery that methyl ethers also function as proficient directing groups under the optimised conditions, potentially also acting as hydrogen bond acceptors. This finding has the promise to dramatically expand the applicability of our ion‐paired chiral catalysts.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes ; day:29 ; month:02 ; year:2024 ; extent:8
Angewandte Chemie / International edition. International edition ; (29.02.2024) (gesamt 8)
- Creator
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Paterson, Kieran J.
Dahiya, Amit
Williams, Benjamin D.
Phipps, Robert J.
- DOI
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10.1002/anie.202317489
- URN
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urn:nbn:de:101:1-2024022914503884688249
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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14.08.2025, 10:52 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Paterson, Kieran J.
- Dahiya, Amit
- Williams, Benjamin D.
- Phipps, Robert J.
Other Objects (12)
Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes
Chemoselective nucleophilic α-amination of amides
Rhodium-Catalyzed Diastereoselective Intermolecular C-H Amination
A Rhodium-Catalyzed “Hook-and-Slide” Homologation of Amides
Synthesis of Heterocycles Based on Rhodium-Catalyzed C–H Amination
Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines
Asymmetric synthesis of γ-branched amines via rhodium-catalyzed reductive amination
Azide–Enolate Cycloaddition‐Rearrangement Enables Direct α‐Amination of Amides and Enelactam Synthesis from Esters **
Microwave‐Assisted Reductive Amination of Aldehydes and Ketones Over Rhodium‐Based Heterogeneous Catalysts
Kinetic modeling of rhodium‐catalyzed reductive amination of undecanal in different solvent systems
Kinetic Modeling of Rhodium‐Catalyzed Reductive Amination of Undecanal in Different Solvent Systems
Directing poiesis
Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes
Chemoselective nucleophilic α-amination of amides
Rhodium-Catalyzed Diastereoselective Intermolecular C-H Amination
A Rhodium-Catalyzed “Hook-and-Slide” Homologation of Amides
Synthesis of Heterocycles Based on Rhodium-Catalyzed C–H Amination
Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines
Asymmetric synthesis of γ-branched amines via rhodium-catalyzed reductive amination
Azide–Enolate Cycloaddition‐Rearrangement Enables Direct α‐Amination of Amides and Enelactam Synthesis from Esters **
Microwave‐Assisted Reductive Amination of Aldehydes and Ketones Over Rhodium‐Based Heterogeneous Catalysts
Kinetic modeling of rhodium‐catalyzed reductive amination of undecanal in different solvent systems
Kinetic Modeling of Rhodium‐Catalyzed Reductive Amination of Undecanal in Different Solvent Systems
Directing poiesis
Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes
Chemoselective nucleophilic α-amination of amides
Rhodium-Catalyzed Diastereoselective Intermolecular C-H Amination
A Rhodium-Catalyzed “Hook-and-Slide” Homologation of Amides
Synthesis of Heterocycles Based on Rhodium-Catalyzed C–H Amination
Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines
Asymmetric synthesis of γ-branched amines via rhodium-catalyzed reductive amination
Azide–Enolate Cycloaddition‐Rearrangement Enables Direct α‐Amination of Amides and Enelactam Synthesis from Esters **
Microwave‐Assisted Reductive Amination of Aldehydes and Ketones Over Rhodium‐Based Heterogeneous Catalysts
Kinetic modeling of rhodium‐catalyzed reductive amination of undecanal in different solvent systems
Kinetic Modeling of Rhodium‐Catalyzed Reductive Amination of Undecanal in Different Solvent Systems