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A new photoremovable protecting group : synthesis and reaction mechanism

Kamdzhilov, Yavor. A new photoremovable protecting group : synthesis and reaction mechanism. 2006, Doctoral Thesis, University of Basel, Faculty of Science.

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Official URL: http://edoc.unibas.ch/diss/DissB_7677

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Abstract

A new photoremovable protecting group, allowing for irradiation up to 400 nm, is introduced. A simple synthetic route to three derivatives was described and their photochemistry in aqueous solutions and acetonitrile was investigated. Quantum yields of substrate deprotection Фdep (HBr, CH3COOH and HOPO(OEt)2) were measured spectrophotometrically and by HPLC and were found to be satisfactory (Φ = 0.3 – 0.7). Nucleofugacity of the leaving group, the nature of solvent, and the pH determine the reaction mechanism. A reactive intermediate, expelling the protected substrate, was detected by laser flash photolysis (LFP) and by time-resolved infrared spectroscopy (TRFTIR), and the release rate constants of substrates were found to be in the microsecond time-domain. A mechanistic scheme rationalizing our observation is proposed.
Advisors:Wirz, Hans-Jakob
Committee Members:Giese, Bernd
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Giese, Bernd
Item Type:Thesis
Thesis Subtype:Doctoral Thesis
Thesis no:7677
Thesis status:Complete
Number of Pages:83
Language:English
Identification Number:
Last Modified:22 Jan 2018 15:50
Deposited On:13 Feb 2009 15:47

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