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Updated: Feb 22, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Formal Diels-Alder reaction of saturated carboxylic acids via C-H activation
Qiyuan He1, Yilin Lu1, Tao Sheng1
1Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA.
Abstract:
Constructing ubiquitous bridged bicyclic scaffolds from simple aliphatic feedstocks via multiple C(sp3)-H functionalizations is a significant challenge in organic synthesis, demanding powerful catalysts capable of precise selectivity control. Here we demonstrate a catalytic system that enables abundant cyclic carboxylic acids to couple with dienophiles in a formal Diels-Alder manner with exclusive regioselectivity, forging bridged bicyclic scaffolds. Mechanistic studies revealed that the pyridine-pyridone ligand plays a crucial role in the β,γ-dehydrogenation of cyclic carboxylic acids, concerted decarboxylation process and subsequent regioselective β-hydride elimination through precise control of the electronic distribution of palladium and cyclic carboxylic acids and the steric interactions between them. Dienes generated in situ are rapidly intercepted by a variety of dienophiles, furnishing the bridged bicyclic motifs with exclusive endoselectivity. Notably, β-, γ- and δ-methylene C(sp3)-H bonds are functionalized with exclusive regioselectivity controlled by one catalyst.
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