Dynamic Kinetic Resolution of 2‐(Quinolin‐8‐yl)Benzaldehydes: Atroposelective Iridium‐Catalyzed Transfer Hydrogenative Allylation

An atroposelective Ir‐catalyzed dynamic kinetic resolution (DKR) of 2‐(quinolin‐8‐yl)benzaldehydes/1‐naphthaldehydes by transfer hydrogenative coupling of allyl acetate is disclosed. The allylation reaction takes place with simultaneous installation of central and axial chirality, reaching high dias...

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Bibliographic Details
Published in:Angewandte Chemie 2023-08, Vol.135 (35), p.n/a
Main Authors: Carmona, José A., Rodríguez‐Salamanca, Patricia, Fernández, Rosario, Lassaletta, José M., Hornillos, Valentín
Format: Article
Language:English
Subjects:
Acetic acid
Aldehydes
Allyl compounds
Allylation
Asymmetric Catalysis
Axial Chirality
Carbonyl compounds
Carbonyl groups
Carbonyls
Catalysts
Chemical reactions
Chemistry
Chirality
Iridium
Iridium Catalysis
Lewis acid
Quinoline
Quinolines
Racemization
Substrates
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Summary:An atroposelective Ir‐catalyzed dynamic kinetic resolution (DKR) of 2‐(quinolin‐8‐yl)benzaldehydes/1‐naphthaldehydes by transfer hydrogenative coupling of allyl acetate is disclosed. The allylation reaction takes place with simultaneous installation of central and axial chirality, reaching high diastereoselectivities and excellent enantiomeric excesses when ortho‐cyclometalated iridium‐DM‐BINAP is used as the catalyst. The racemization of the substrates occurs through a designed transient Lewis acid‐base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group. A designed transient Lewis pair interaction was found to be the key to facilitate the racemization of 8‐arylquinoline‐2‐formaldehydes and enable an iridium‐catalyzed dynamic kinetic resolution, accomplished via atroposelective allylation by transfer hydrogenative coupling.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202306981