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

Thomas Field, Julie Peterson, Chicheng Ma, Pradeepkumar Jagadesan, José P. Da Silva, Marina Rubina, V. Ramamurthy, Richard S. Givens

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish (US)
Pages (from-to)1364-1372
Number of pages9
JournalPhotochemical and Photobiological Sciences
Volume19
Issue number10
DOIs
StatePublished - Oct 2020

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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