Skip to content

Research at St Andrews

An all-purpose preparation of oxime carbonates and resultant insights into the chemistry of alkoxycarbonyloxyl radicals

Research output: Contribution to journalArticle

DOI

Author(s)

Roy Thomas McBurney, Andrew D. Harper, Alexandra Martha Zoya Slawin, John Christopher Walton

School/Research organisations

Abstract

Oxime carbonates have been synthesised and their potential studied as a new class of radical precursor. A general synthetic route, avoiding laboratory use of phosgene, was developed. Alkyl or aryl 1H-imidazole-1-carboxylates were prepared from the corresponding alcohols and 1,1-carbonyldiimidazole, then reacted with oximes in the presence of base. UV photolyses of oxime carbonates released particular N- and O-centred radicals suitable for spectroscopic examination. Spiro-cyclisations of alkoxycarbonyloxyl radicals onto aromatic acceptors and 5-exo cyclisations onto alkene acceptors were studied by EPR spectroscopy. EPR data also provided insight to the loss of CO2 from alkoxycarbonyloxyl radicals. The conformational preferences of 2-oxo-1,3-dioxolan-4-yl-methyl and related radicals were established. Modest yields of cyclic carbonates were obtained from preparative scale photolyses.

Close

Details

Original languageEnglish
Pages (from-to)3436-3444
Number of pages9
JournalChemical Science
Volume3
Issue number12
DOIs
StatePublished - Dec 2012

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Rapid and Selective Spiro-Cyclisations of O-Centred Radicals onto Aromatic Acceptors

    Walton, J. C., McBurney, R. T., Eisenschmidt, A. & Slawin, A. M. Z. Mar 2013 In : Chemical Science. 4, p. 2028-2035 8 p.

    Research output: Contribution to journalArticle

  2. UV promoted phenanthridine syntheses from oxime carbonate derived iminyl radicals

    McBurney, R. T., Slawin, A. M. Z., Smart, L. A., Yu, Y. & Walton, J. C. 2011 In : Chemical Communications. 47, 28, p. 7974-7976 3 p.

    Research output: Contribution to journalArticle

  3. Approach to 3-aminoindolin-2-ones via oxime ether functionalized carbamoylcyclohexadienes

    Bella, A. F., Slawin, A. M. Z. & Walton, J. C. 3 Sep 2004 In : Journal of Organic Chemistry. 69, p. 5926-5933 8 p.

    Research output: Contribution to journalArticle

Related by journal

  1. A new route to N-aromatic heterocycles from the hydrogenation of diesters in the presence of anilines

    Shi, Y., Kamer, P. C. J., Cole-Hamilton, D. J., Harvie, M., Baxter, E. F., Lim, K. J. C. & Pogorzelec, P. 1 Oct 2017 In : Chemical Science. 8, 10, p. 6911-6917

    Research output: Contribution to journalArticle

  2. Sonogashira diversification of unprotected halotryptophans, halotryptophan containing tripeptides; and generation of a new to nature bromo-natural product and its diversification in water

    Corr, M. J., Sharma, S. V., Pubill Ulldemolins, C., Bown, R. T., Poirot, P., Smith, D. R. M., Cartmell, C., Abou Fayad, A. & Goss, R. J. M. 1 Mar 2017 In : Chemical Science. 8, 3, p. 2039-2046 8 p.

    Research output: Contribution to journalArticle

  3. pH controlled assembly of a self-complementary halogen-bonded dimer

    Maugeri, L., Jamieson, E., Cordes, D. B., Slawin, A. M. Z. & Philp, D. 1 Feb 2017 In : Chemical Science. 8, 2, p. 938-945

    Research output: Contribution to journalArticle

  4. Non-bonding 1,5-S•••O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles

    Robinson, E. R. T., Walden, D. M., Fallan, C., Greenhalgh, M. D., Cheong, P. H-Y. & Smith, A. D. 1 Dec 2016 In : Chemical Science. 7, 12, p. 6919-6927 9 p.

    Research output: Contribution to journalArticle

  5. Circulatory zinc transport is controlled by distinct interdomain sites on mammalian albumins

    Handing, K. B., Shabalin, I. G., Kassaar, O., Khazaipoul, S., Blindauer, C. A., Stewart, A. J., Chruszcz, M. & Minor, W. 1 Nov 2016 In : Chemical Science. 7, 11, p. 6635-6648 14 p.

    Research output: Contribution to journalArticle

ID: 42242627