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Kang, H. Allene Synthesis. Encyclopedia. Available online: https://encyclopedia.pub/entry/60272 (accessed on 03 October 2026).
Kang H. Allene Synthesis. Encyclopedia. Available at: https://encyclopedia.pub/entry/60272. Accessed October 03, 2026.
Kang, Helena. "Allene Synthesis" Encyclopedia, https://encyclopedia.pub/entry/60272 (accessed October 03, 2026).
Kang, H. (2026, September 23). Allene Synthesis. In Encyclopedia. https://encyclopedia.pub/entry/60272
Kang, Helena. "Allene Synthesis." Encyclopedia. Web. 23 September, 2026.
Allene Synthesis
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Allenes are cumulenes containing two consecutive carbon–carbon double bonds (C=C=C) whose terminal substituents lie in orthogonal planes. Allene synthesis is the set of transformations that install this 1,2-diene array. One established route is the propargyl Claisen rearrangement, in which a propargylic vinyl ether undergoes a 3,3-sigmatropic reorganization to an allenic carbonyl derivative [1]. Radical processes generate the cumulene by addition–elimination or hydrogen-atom transfer sequences that terminate in an allenic radical or closed-shell allene [2]. Fragmentative constructions create the two double bonds by scission of a C–C bond in a suitably disposed precursor, releasing the allene as the unsaturated fragment [3]. SN2' displacement of a propargylic leaving group by an organometallic nucleophile likewise produces a substituted allene. The defining structural criterion is the cumulative C=C=C unit, which distinguishes allenes from isolated dienes, conjugated 1,3-dienes, and alkynes. Axial chirality arises when the four termini are appropriately substituted, so stereochemical control is an intrinsic feature of many allene-forming bond reorganizations.

allene synthesis cumulene SN2' substitution C–C fragmentation

References

  1. David Tejedor; Gabriela Méndez-Abt; Leandro Cotos; Fernando García-Tellado; Propargyl Claisen rearrangement: allene synthesis and beyond. Chem. Soc. Rev. 2012, 42, 458-471. [CrossRef]
  2. Yajun Li; Hongli Bao; Radical transformations for allene synthesis. Chem. Sci. 2022, 13, 8491-8506. [CrossRef]
  3. Robert V. Kolakowski; Madhuri Manpadi; Yue Zhang; Thomas J. Emge; Lawrence J. Williams; Allene Synthesis via C−C Fragmentation: Method and Mechanistic Insight. J. Am. Chem. Soc. 2009, 131, 12910-12911. [CrossRef]
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Subjects: Chemistry, Organic
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Update Date: 23 Sep 2026
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