Copper-catalyzed asymmetric allylic C–H amination of alkenes using N-arylhydroxylamines

The first copper-catalyzed asymmetric allylic C–H amination of alkenes using N-arylhydroxylamines as aminating agents is disclosed. Enantioselective C–N bond formation reactions are promoted in the presence of Cu(MeCN)4PF6 as a pre-catalyst and R-(+)-BINAM as a chiral ligand. This protocol delivers...

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Bibliographic Details
Published in:Organic chemistry frontiers an international journal of organic chemistry 2021-01, Vol.8 (13), p.3228-3237
Main Authors: Murru, Siva, Mokar, Bhanudas D, Bista, Ramesh, Harakat, Dominique, Jean Le Bras, Fronczek, Frank, Nicholas, Kenneth M, Srivastava, Radhey S
Format: Article
Language:English
Subjects:
Alkenes
Amination
Aromatic compounds
Asymmetry
Bonding
Catalysis
Catalysts
Chemical Sciences
Computer applications
Coordination compounds
Copper
Crystallography
Enantiomers
High-performance liquid chromatography
Ligands
NMR
Nuclear magnetic resonance
Organic chemistry
Stereoselectivity
Structural analysis
X-ray crystallography
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Summary:The first copper-catalyzed asymmetric allylic C–H amination of alkenes using N-arylhydroxylamines as aminating agents is disclosed. Enantioselective C–N bond formation reactions are promoted in the presence of Cu(MeCN)4PF6 as a pre-catalyst and R-(+)-BINAM as a chiral ligand. This protocol delivers chiral N-aryl allylamines in good yields and enantioselectivities. Data regarding the effect of ligand structure and solvents on the efficiency and enantioselectivity of amination reactions are presented. Furthermore, isolation of the metal–ligand–nitroso complex, ESI-MS reaction monitoring analysis and computational calculations provided additional insights into the mechanistic pathway. DFT modeling of the reaction pathway suggests that the stereoselectivity is determined in the conversion of (BINAM)Cu(PhNO)(η2-alkene)+ to (BINAM)Cu(N-aryl allylhydroxylamine) via a concerted, asynchronous transition state for C–N bond formation. This catalytic approach features operational simplicity, high product yields with good enantioselectivity, and no byproducts except for water. [Formula Omitted]
ISSN:2052-4110
2052-4110
DOI:10.1039/d1qo00223f