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Competing pathways for photoremovable protecting groups: the effects of solvent, oxygen and encapsulation

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Abstract

Extending the applications of Photoremovable Protecting Groups (PPGs) to “cage” phenols has generally met with unusually complex PPG byproducts. In this study, we demonstrate that the p-hydroxyphenacyl (pHP) cage for both simple and complex phenolics, including tyrosine, dispenses free phenols. With the simpler unsubstituted phenols, the reaction is governed by their Brønsted Leaving Group ability. On the other hand, the byproducts of the cage vary with these phenols. For the more acidic phenols the cage byproduct follows the Favorskii rearrangement to form p-hydroxyphenylacetic acid whereas for the weaker phenols other reactions such as reduction and hydrolysis begin to emerge. When the photolysis is conducted in octa acid (OA) containers, non-Favorskii, unrearranged fragments of the cage and other byproducts arise.

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Authors and Affiliations

  1. Department of Chemistry, University of Kansas, Lawrence, KS, 66045, USA

    Thomas Field, Julie Peterson, Chicheng Ma, Marina Rubina & Richard S. Givens

  2. Department of Chemistry, University of Miami, Coral Gabies, FL, 33124, USA

    Pradeepkumar Jagadesan & V. Ramamurthy

  3. CCMAR - Centre of Marine Sciences, University of Algarve, Campus de Gambelas, 8005-139, Faro, Portugal

    José P. Da Silva

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  1. Thomas Field
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  2. Julie Peterson
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  3. Chicheng Ma
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  5. José P. Da Silva
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  6. Marina Rubina
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  7. V. Ramamurthy
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Correspondence to José P. Da Silva.

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Electronic supplementary information (ESI) available: Experimental procedures, 1H NMR, UV and ESI-MS spectra for all new compounds. Irradiation procedures, 1H NMR titration spectra of host–guest complexes, progress of photoreactions as monitored by 1H NMR, LC-DAD-MS. See DOI: 10.1039/d0pp00067a

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Field, T., Peterson, J., Ma, C. et al. Competing pathways for photoremovable protecting groups: the effects of solvent, oxygen and encapsulation. Photochem Photobiol Sci 19, 1364–1372 (2020). https://doi.org/10.1039/d0pp00067a

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