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Flash photolytic release of alcohols from photolabile carbamates or carbonates is rate-limited by decarboxylation of the photoproduct

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Abstract

Flash photolysis of a 7-nitroindolinyl carbamate derivative in neutral aqueous solution rapidly generated a monoalkyl carbonate salt. The rate constant for subsequent decarboxylation of this salt [mono(2-phosphoryloxyethyl) carbonate], determined by rapid scan IR difference spectroscopy, was 0.4 s-1 at pH 7.0, 20 ◦C. This rate reflects release of the product alcohol upon photolysis of the parent compound. In general, alcohols protected as photolabile carbamate (or carbonate) derivatives will therefore be released too slowly for studies of the kinetics of millisecond time scale biological processes.

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Authors and Affiliations

  1. National Institute for Medical Research, The Ridgeway, Mill Hill, London, UK, NW7 1AA

    George Papageorgiou & John E. T. Corrie

  2. Department of Biochemistry and Biophysics, The Arrhenius Laboratories for Natural Sciences, Stockholm University, SE-106 91, Stockholm, Sweden

    Andreas Barth

Authors
  1. George Papageorgiou
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  2. Andreas Barth
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  3. John E. T. Corrie
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Correspondence to John E. T. Corrie.

Additional information

Electronic supplementary information (ESI) available: Figs. S1 and S2. See http://www.rsc.org/suppdata/pp/b4/b417153e/

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Papageorgiou, G., Barth, A. & Corrie, J.E.T. Flash photolytic release of alcohols from photolabile carbamates or carbonates is rate-limited by decarboxylation of the photoproduct. Photochem Photobiol Sci 4, 216–220 (2005). https://doi.org/10.1039/b417153e

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