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Updated: Nov 2, 2025
Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
A borane-mediated palladium-catalyzed reductive allylic alkylation of α,β-unsaturated carbonyl compounds
Barry M Trost1, Zhijun Zuo1, Johnathan E Schultz1
1Departmentof Chemistry, Stanford University Stanford CA 94305-5080 USA bmtrost@stanford.edu.
Abstract:
The development of the palladium-catalyzed allylic alkylation of in situ generated boron enolates via tandem 1,4-hydroboration is reported. Investigation of the reaction revealed insights into specific catalyst electronic features as well as a profound leaving group effect that proved crucial for achieving efficient allylic alkylation of ester enolates at room temperature and ultimately a highly preparatively useful synthesis of notoriously challenging acyclic all-carbon quaternary stereocenters. The method demonstrates boron enolates as viable pro-nucleophiles in transition-metal catalyzed allylic alkylation, potentially opening up further transformations outside their traditional use.
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