Vývoj fotolabilních chránících skupin

Mgr. Jaromír Literák, Ph.D.

Doctoral thesis

Development of photoremovable protecting group

Abstract:

The objective of this thesis is to contribute to the development and applications of the photolabile protecting groups (PPGs). The first chapter contains a short review dealing with the most important photoremovable protecting groups and photolinkers. It is aimed to provide the reader the newest facts concerning the reaction mechanisms and PPG applications. The following chapter summarizes our results. We exploited the photochemical behavior of 2-alkylphenyl ketones, which has been thoroughly studied in our research group since 2000 when Petr Klán proposed 2,5-dimethylphenacyl (DMP) chromophore as a photoremovable protecting group for carboxylic acids. We successfully applied the DMP chromophore to mask alcohols and phenols, the development of new photolabile linker, which contains 2-methylphenacyl moiety, is described. Short section is devoted to the photoenolisation of cyclic ketones, 4,7-dimethylindan-1-one and 4,7-dimethylindan-1,3-dione. In addition, we wished to improve properties of our protecting groups, namely their solubility in aqueous solutions. We decided to prepare heterocyclic, pyridine-derived, analogues of the phenacyl and 2-methylphenacyl esters. However, early experiments with m-pyridacyl ester prompted us to reinvestigate the reaction mechanism of reductive cleavage of the phenacyl and pyridacyl carboxylates in alcohols. The work, which is described in the last section of the second chapter, revealed that the reaction mechanism known up to date required corrections. The experimental procedures and product identification are provided in third chapter. Most of the results have been already published in three papers, which are attached as three Appendices.

Keywords

Photolabile protecting groups, photolabile linkers, photoenolisation, phenacyl protecting group

Language used: Czech

Date on which the thesis was submitted / produced: 27. 2. 2006

Thesis defence

• Date of defence: 27. 2. 2006
• Supervisor: prof. RNDr. Petr Klán, Ph.D.

Masaryk University

Faculty of Science

Doctoral programme / field:
Chemistry / Organic Chemistry