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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| Published in: | Chemical communications (Cambridge, England) Vol. 61; no. 34; p. 6275 |
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| Main Authors: | , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
England
22.04.2025
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| ISSN: | 1364-548X, 1364-548X |
| Online Access: | Get more information |
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| Summary: | 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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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 ObjectType-Review-3 content type line 23 |
| ISSN: | 1364-548X 1364-548X |
| DOI: | 10.1039/d4cc06332e |