Acetoxy allenoates as emerging synthons in annulation/cycloaddition reactions

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 diff...

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Vydáno v:Chemical communications (Cambridge, England) Ročník 61; číslo 34; s. 6275
Hlavní autoři: Kumara Swamy, K C, Chauhan, Sachin, Sanjeeva Kumar, A
Médium: Journal Article
Jazyk:angličtina
Vydáno: England 22.04.2025
ISSN:1364-548X, 1364-548X
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Shrnutí: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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ISSN:1364-548X
1364-548X
DOI:10.1039/d4cc06332e