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Unusually Facile Thermal Homodienyl-[1,5]-Hydrogen Shift Reactions in Photochemically-Generated Vinyl Aziridines

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)11429-11434
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number32
Early online date6 Jul 2016
DOIs
DateAccepted/In press - 20 Apr 2016
DateE-pub ahead of print - 6 Jul 2016
DatePublished (current) - 1 Aug 2016

Abstract

A range of photochemically-generated tri- and tetracyclic vinyl aziridines have been found to undergo a general and surprisingly low temperature ring opening via a [1,5]-hydrogen shift reaction. The rate of the process was found to be highly dependent on structure and substitution around the azirdine ring and the alkene terminus, with some substrates being observed to undergo ring opening at temperatures as low as 25˚C. The rigid nature of these polycyclic systems precludes a conformational explanation these rate differences and an Eyring study confirmed a negligible entropic barrier to the reaction. However, the Eyring plots for two different aziridines systems showed a significant difference in their enthalpies of activation. It is therefore believed that the levels of aziridine ring strain, as well as electronic effects, are the dominant factors in this sequence.

    Research areas

  • aziridine, photochemistry, reaction kinetics, rearrangement, sigmatropic

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  • Final manuscript with corrections

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via Wiley at http://onlinelibrary.wiley.com/wol1/doi/10.1002/chem.201600479/abstract. Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 1 MB, PDF document

    Licence: CC BY-NC

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