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Updated: May 16, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Acetoxy allenoates as emerging synthons in annulation/cycloaddition reactions
K C Kumara Swamy1, Sachin Chauhan1, A Sanjeeva Kumar1
1School of Chemistry, University of Hyderabad, Hyderabad 500 046, Telangana, India. kckssc@uohyd.ac.in.
Abstract:
In contrast to the normal allenoates (2,3-butadienoates) that undergo phosphine/amine addition generating dipolar-type intermediates, acetoxy allenoates that contain a facile-leaving -OAc group create electrophilic diene-phosphonium/ammonium intermediates rendering the reactivity pattern vastly different in the two cases. This review highlights the fascinating chemistry of acetoxy allenoates and related substrates. The diene-phosphonium/ammonium intermediate thus formed from acetoxy allenoate [substituted 5-acetoxypenta-2,3-dienoate or 2-(acetoxymethyl)buta-2,3-dienoate] participates in a plethora of cycloaddition/annulation reactions with bisnucleophiles generating multifunctional hetero- or homo-cycles in very few steps. Thus the electron-withdrawing effect of the phosphonium as well as carboxylate groups, making the diene-phosphonium/ammonium intermediates quite electrophilic, has been pivotal to the growth and significant interest during the last 10-15 years in this emerging class of substrates as revealed in this article. A comparison of this chemistry with that of (acetoxy)(acyl)allenes and allenyl acetates is also made briefly.
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