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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Activation of alcohols with carbon dioxide: intermolecular allylation of weakly acidic pronucleophiles
Simon B Lang1, Theresa M Locascio, Jon A Tunge
1Department of Chemistry, The University of Kansas , 2010 Malott Hall, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, United States.
Abstract:
The direct coupling of allyl alcohols with nitroalkanes, nitriles, and aldehydes using catalytic Pd(PPh3)4 has been accomplished via activation of C-OH bonds with CO2. The in situ formation of carbonates from alcohols and CO2 facilitates oxidative addition to Pd to form reactive π-allylpalladium intermediates. In addition, the formation of a strong base activates nucleophiles toward the reaction with the π-allylpalladium electrophile. Overall, this atom economical reaction provides a new C-C bond without the use of an external base and generates water as the only byproduct.
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