Et<sub>3</sub>B-mediated palladium-catalyzed direct allylic substitution reactions of Morita–Baylis–Hillman alcohols with aromatic amines

Nickel complexes bearing chiral diphosphine ligands, such as (S)-Tol-MeO-BIPHEP and (S)-H 8 -BINAP, serve as efficient catalysts for asymmetric allylic alkylation (AAA) of β-ketoesters using allylic amines as allyl sources. The reactions proceed with high catalytic activity and high enantioselectivity. N-Methyl-N-phenyl allylic amines were indispensable to achieve the high catalytic activity and high enantioselectivity, and to expand the substrate scope to 5-and 7-membered β-ketoesters, whose nickel-catalyzed AAA with allylic alcohols results in low enantioselectivity. On the basis of the kinetics using a catalyst system made of Ni(cod) 2 and (S)-Tol-MeO-BIPHEP, and DFT calculations for the reaction pathway of the AAA reaction mediated by an isolated olefin-coordinated nickel-DPPF complex 4b, we propose a mechanism where protonation of the nitrogen atom of the coordinating allylic amine by β-ketoester is key to cleaving the C-N bond and delivering a cationic π-allyl nickel(II) intermediate. ASSOCIATED CONTENT Supporting InformationDetails of experimental procedures, optimization of reaction conditions, kinetic studies, NMR spectra, HPLC chart for all new compounds, and Cartesian coordinates of DFT-computed structures (PDF) were included in a Supporting Information. X-ray crystallographic data for complex 4b (CIF).

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Et₃B-mediated palladium-catalyzed direct allylic substitution reactions of Morita–Baylis–Hillman alcohols with aromatic amines

Cited by 3 publications

References 22 publications

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Et3B-mediated palladium-catalyzed direct allylic substitution reactions of Morita–Baylis–Hillman alcohols with aromatic amines

Cited by 3 publications

References 22 publications

Controlled and diastereoselective synthesis of α-(3-hydroxy-2 oxoindolin-3-yl)-β-aminopropanoates

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Direct nucleophilic substitutions of allylic alcohols with 1,3-dicarbonyl compounds: Synthetic design, mechanistic aspects and applications

Asymmetric Allylic Alkylation of β-Ketoesters via C–N Bond Cleavage of N-Allyl-N-methylaniline Derivatives Catalyzed by a Nickel–Diphosphine System

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Et₃B-mediated palladium-catalyzed direct allylic substitution reactions of Morita–Baylis–Hillman alcohols with aromatic amines