Nickel-Catalyzed Asymmetric Allylic Alkylation of β-Dicarbonyl Compounds via C-C Bond Activation of 2-Allylated Cyclic 1,3-Diketones
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
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Higashida et al - 2023 - Nickel-Catalyzed Asymmetric Allylic Alkylation _C-C_AAA_ACSCatal-R3.pdf (986.77 Ko)
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cs2c05664_si_001.pdf (5.59 Mo)
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