Rapid Access to Conjugated Z,Z,Z-Trienes

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dc.contributor.authorTon, N.N.H.
dc.contributor.authorMai, B.K.
dc.contributor.authorFallon, T.
dc.contributor.authorNguyen, T.V.
dc.date.issued2025
dc.description.abstractIntercepting reactions have recently emerged as an innovative approach in organic synthesis, allowing chemists to harness reactive intermediates to access structures and functionalities that conventional methods cannot easily achieve. By deliberately manipulating reaction pathways, this strategy provides a unique avenue to explore unusual reactivities and complex molecular architectures. In this work, we have developed a new protocol for the nucleophile-intercepted Beckmann fragmentation reaction (NuBFr). Employing tropone oxime tosylate – a simple and readily accessible precursor – and a diverse set of nucleophiles generated in situ from alcohols, phenols, thiols and alkynes with strong bases, we successfully synthesized a library of novel conjugated Z,Z,Z-trienecarbonitrile derivatives. This method facilitates rapid access to the conjugated Z,Z,Z-triene motif, a structural feature rarely encountered in synthetic chemistry. Our computational studies indicate that the NuBFr reaction likely proceeds through the formation of a bicylic azirine intermediate. The resulting Z,Z,Z-trienecarbonitriles could undergo an unprecedented thermally induced 8π/6π/4π electrocyclization cascade sequence to produce trisubstituted olefins. This sequence underscores the fundamental value of these motifs in pushing the boundaries of unusual reactivities in organic synthesis.
dc.description.statementofresponsibilityNhan Nu Hong Ton, Binh Khanh Mai, Thomas Fallon, Thanh Vinh Nguyen
dc.identifier.citationAngewandte Chemie International Edition, 2025; 64(22):e202502713-1-e202502713-8
dc.identifier.doi10.1002/anie.202502713
dc.identifier.issn1433-7851
dc.identifier.issn1521-3773
dc.identifier.orcidFallon, T. [0000-0002-6495-5282]
dc.identifier.urihttps://hdl.handle.net/2440/147326
dc.language.isoen
dc.publisherWiley
dc.relation.granthttp://purl.org/au-research/grants/arc/DP200100063
dc.rights© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
dc.source.urihttps://doi.org/10.1002/anie.202502713
dc.subjectBeckmann fragmentation
dc.subjectConjugation
dc.subjectInterrupted reaction
dc.subjectPolyene
dc.subjectTriene
dc.titleRapid Access to Conjugated Z,Z,Z-Trienes
dc.typeJournal article
pubs.publication-statusPublished

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