Nickel-Catalyzed Asymmetric Allylic Alkylation of β-Dicarbonyl Compounds via C-C Bond Activation of 2-Allylated Cyclic 1,3-Diketones - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue ACS Catalysis Année : 2023

Nickel-Catalyzed Asymmetric Allylic Alkylation of β-Dicarbonyl Compounds via C-C Bond Activation of 2-Allylated Cyclic 1,3-Diketones

K. Higashida
  • Fonction : Auteur
V. Smaïl
  • Fonction : Auteur
H. Nagae
  • Fonction : Auteur correspondant
K. Mashima
  • Fonction : Auteur correspondant

Résumé

The asymmetric allylic alkylation (AAA) reaction using less reactive, stable allylic sources is challenging. We achieved a nickel(0)- catalyzed AAA reaction of β-dicarbonyl compounds under ambient conditions through unstrained C.C bond activation of 2-allylated 2- methylcyclohexane-1,3-dione derivatives to afford the corresponding quaternary chiral compounds in high yield with high enantioselectivity. The reaction proceeded almost irreversibly due to the low solubility of the side-product, 2-methylcyclohexane-1,3-dione. Control experiments and DFT calculations allowed for the elucidating the mechanism of the AAA reaction with the Ni(0)-(S)-tol-MeO-BIPHEP catalyst system; the turnover limiting step is C.C bond formation, and the reverse reaction requires 7.6 kcal mol.1 higher activation energy than the forward reaction. © 2023 American Chemical Society.

Domaines

Chimie
Fichier principal
Vignette du fichier
Higashida et al - 2023 - Nickel-Catalyzed Asymmetric Allylic Alkylation _C-C_AAA_ACSCatal-R3.pdf (986.77 Ko) Télécharger le fichier
cs2c05664_si_001.pdf (5.59 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-04018993 , version 1 (12-07-2023)

Licence

Paternité - Pas d'utilisation commerciale

Identifiants

Citer

K. Higashida, V. Smaïl, H. Nagae, J.-F. Carpentier, K. Mashima. Nickel-Catalyzed Asymmetric Allylic Alkylation of β-Dicarbonyl Compounds via C-C Bond Activation of 2-Allylated Cyclic 1,3-Diketones. ACS Catalysis, 2023, 13 (3), pp.2156-2161. ⟨10.1021/acscatal.2c05664⟩. ⟨hal-04018993⟩
36 Consultations
31 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More