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trans-Cyclooctene
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<h2 id="preparation">Preparation</h2> <p><i>trans</i>-Cyclooctene was first synthesized on a preparatory scale by <a href="/facts/Arthur_C._Cope/1xV4KlH4">Arthur C. Cope</a> with a <a href="/facts/Hofmann_elimination/yPhnFkXK">Hofmann elimination</a> reaction of <i>N,N,N</i>-trimethylcyclooctylammonium iodide.<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> The reaction gives a mixture of <i>cis</i> and <i>trans</i> isomers, and the <i>trans</i> isomer is selectively <a href="/facts/Chemical_trap/NUoApMRS">trapped</a> as a <a href="/facts/Coordination_complex/1tCyeQUm">complex</a> with <a href="/facts/Silver_nitrate/U5w4A3DN">silver nitrate</a>. </p><p>Other methods exist where the <i>trans</i> isomer is synthesized from the <i>cis</i> isomer in several synthetic steps. For instance, it can be prepared in almost 100% yield by converting the <i>cis</i> isomer to 1,2-epoxycyclooctane ("cyclooctene oxide") followed by reactions with <a href="/facts/Lithium_diphenylphosphide/4grep8IN">lithium diphenylphosphide</a> (LiPPh2) and with <a href="/facts/Methyl_iodide/uUKdue80">methyl iodide</a> CH3I. (Similar procedures can give <i>cis</i>,<i>trans</i> isomers of 1,4-cyclooctadiene and <a href="/facts/1,5-cyclooctadiene/NjXGaL8t">1,5-cyclooctadiene</a>).<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> </p><p>In addition, a <a href="/facts/Photochemical/GsXNBWon">photochemical</a> method exists for the direct <i>cis</i>–<i>trans</i> isomerisation. Although this equilibrium strongly favours the more stable <i>cis</i> form, the reaction can be driven towards the <i>trans</i> form by trapping with silver ions.<a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a><a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> </p> <h2 id="reactions">Reactions</h2> <p>Because of the higher internal strain on the double bond, the <i>trans</i> isomer is more reactive than the <i>cis</i> isomer and of typical unsaturated hydrocarbons. For instance, its double bond will rapidly <a href="/facts/Addition_reaction/LvIngK0g">add</a> <a href="/facts/Tetrazine/FxgrNJk3">tetrazine</a> and its derivatives.<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a> The compound also readily polymerizes with a <a href="/facts/Ruthenium/uzCm4ufn">ruthenium</a>-based initiator.<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a> </p> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Neuenschwander, Ulrich; Hermans, Ive (2011). "The conformations of cyclooctene: Consequences for epoxidation chemistry". Journal of Organic Chemistry. 76 (24): 10236–10240. doi:10.1021/jo202176j. PMID 22077196. <a href="/wiki/Journal_of_Organic_Chemistry" target="_blank">/wiki/Journal_of_Organic_Chemistry</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Walker, Ron; Conrad, Rosemary M.; Grubbs, Robert H. (2009). "The Living ROMP of trans-Cyclooctene". Macromolecules. 42 (3): 599–605. Bibcode:2009MaMol..42..599W. doi:10.1021/ma801693q. PMC 2850575. PMID 20379393. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2850575" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2850575</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Selvaraj, Ramajeyam; Fox, Joseph M. (2013). "trans-Cyclooctene — A stable, voracious dienophile for bioorthogonal labeling". Current Opinion in Chemical Biology. 17 (5): 753–760. doi:10.1016/j.cbpa.2013.07.031. PMC 3925366. PMID 23978373. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3925366" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3925366</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Selvaraj, Ramajeyam; Fox, Joseph M. (2013). "trans-Cyclooctene — A stable, voracious dienophile for bioorthogonal labeling". Current Opinion in Chemical Biology. 17 (5): 753–760. doi:10.1016/j.cbpa.2013.07.031. PMC 3925366. PMID 23978373. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3925366" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3925366</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Planar chirality". doi:10.1351/goldbook.P04681 <a href="/wiki/International_Union_of_Pure_and_Applied_Chemistry" target="_blank">/wiki/International_Union_of_Pure_and_Applied_Chemistry</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Cope, Arthur C.; Ganellin, C. R.; Johnson, H. W.; Van Auken, T. V.; Winkler, Hans J. S. (1963). "Molecular Asymmetry of Olefins. I. Resolution of trans-Cyclooctene1-3". Journal of the American Chemical Society. 85 (20): 3276–3279. doi:10.1021/ja00903a049. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Cope, Arthur C.; Mehta, Anil S. (1964). "Molecular Asymmetry of Olefins. II. The Absolute Configuration of trans-Cyclooctene". Journal of the American Chemical Society. 86 (24): 5626–5630. doi:10.1021/ja01078a044. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Steven D. Paget (2001). "(−)-Dichloro(ethylene)(α-methylbenzylamine)platinum(II)". Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rd119. ISBN 0-471-93623-5. <a href="0-471-93623-5" target="_blank">0-471-93623-5</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>Cope, Arthur C.; Ganellin, C. R.; Johnson, H. W.; Van Auken, T. V.; Winkler, Hans J. S. (1963). "Molecular Asymmetry of Olefins. I. Resolution of trans-Cyclooctene1-3". Journal of the American Chemical Society. 85 (20): 3276–3279. doi:10.1021/ja00903a049. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>Cope, Arthur C.; Bach, Robert D. (1969). "trans-Cyclooctene". Organic Syntheses. 49: 39; Collected Volumes, vol. 5, p. 315. <a href="/wiki/Arthur_C._Cope" target="_blank">/wiki/Arthur_C._Cope</a> <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> <li id="fn:11"><p>Vedejs, Edwin; Snoble, Karel A. J.; Fuchs, Philip L. (1973). "Phosphorus betaines derived from cycloheptene and cyclooctene oxides. Inversion of cyclooctene". Journal of Organic Chemistry. 38 (6): 1178–1183. doi:10.1021/jo00946a024. <a href="/wiki/Journal_of_Organic_Chemistry" target="_blank">/wiki/Journal_of_Organic_Chemistry</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li> <li id="fn:12"><p>Swenton, John S. (1969). "Photoisomerization of cis-cyclooctene to trans-cyclooctene". Journal of Organic Chemistry. 34 (10): 3217–3218. doi:10.1021/jo01262a102. <a href="/wiki/Journal_of_Organic_Chemistry" target="_blank">/wiki/Journal_of_Organic_Chemistry</a> <a href="#fnref:12" class="footnote-back-ref">↩</a></p></li> <li id="fn:13"><p>Royzen, Maksim; Yap, Glenn P. A.; Fox, Joseph M. (2008). "A photochemical synthesis of functionalized trans-cyclooctenes driven by metal complexation". Journal of the American Chemical Society. 130 (12): 3760–3761. doi:10.1021/ja8001919. PMID 18321114. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:13" class="footnote-back-ref">↩</a></p></li> <li id="fn:14"><p>Selvaraj, Ramajeyam; Fox, Joseph M. (2013). "trans-Cyclooctene — A stable, voracious dienophile for bioorthogonal labeling". Current Opinion in Chemical Biology. 17 (5): 753–760. doi:10.1016/j.cbpa.2013.07.031. PMC 3925366. PMID 23978373. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3925366" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3925366</a> <a href="#fnref:14" class="footnote-back-ref">↩</a></p></li> <li id="fn:15"><p>Walker, Ron; Conrad, Rosemary M.; Grubbs, Robert H. (2009). "The Living ROMP of trans-Cyclooctene". Macromolecules. 42 (3): 599–605. Bibcode:2009MaMol..42..599W. doi:10.1021/ma801693q. PMC 2850575. PMID 20379393. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2850575" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2850575</a> <a href="#fnref:15" class="footnote-back-ref">↩</a></p></li> </ol>