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

Knowles, Jonathan P. and Booker-Milburn, Kevin I. (2016) Unusually Facile Thermal Homodienyl-[1,5]-Hydrogen Shift Reactions in Photochemically Generated Vinyl Aziridines. Chemistry: A European Journal, 22 (32). pp. 11429-11434. ISSN 0947-6539

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Official URL: https://doi.org/10.1002/chem.201600479

Abstract

A range of photochemically generated tri‐ and tetracyclic vinyl aziridines have been found to undergo a general and surprisingly low temperature ring opening through a [1,5]‐hydrogen shift reaction. The rate of the process was found to be highly dependent on the 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 of 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.

Item Type: Article
Uncontrolled Keywords: aziridine, photochemistry, reaction kinetics, rearrangement, sigmatropic
Subjects: F100 Chemistry
Department: Faculties > Health and Life Sciences > Applied Sciences
Depositing User: Elena Carlaw
Date Deposited: 15 Mar 2019 15:46
Last Modified: 15 Mar 2019 15:46
URI: http://nrl.northumbria.ac.uk/id/eprint/38425

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