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Updated: Jul 6, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Enantioenriched Allylesters via a Copper-Catalyzed Diene Carboesterification with Alkyltrifluoroborates and
Jonathan J Kennedy-Ellis1, Alexis D Kelleher1, Jaffer A Sayeed1
1Chemistry Department, Natural Science Complex, The State University of New York at Buffalo, Buffalo, New York 14260, United States.
Abstract:
The rapid synthesis of a range of enantioenriched allylic esters is enabled by a new 3-component catalytic enantioselective 1,2-carboesterification of readily available dienes with carboxylic acids and potassium alkyltrifluoroborates. The chiral copper catalyst, formed in situ from Cu(OTf)2 and (4S,4'S)-2,2'-(cyclopentane-1,1-diyl)bis(4-phenyl-4,5-dihydrooxazole), is implicated in both the generation of alkyl radicals from the alkyltrifluoroborates as well as the enantioselective formation of C-O bonds. Potassium salts of primary and secondary alkyltrifluoroborates as well as several benzylic trifluoroborates, tert-butyltrifluoroborate, and phenyltrifluoroborate participate in the reaction. The regioselectivity and enantioselectivity are strongly impacted by variations in all of the reaction components, which in turn are thought to impact the C-O bond-forming reductive elimination from a [Cu(III)] intermediate.
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