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Synthesis 2012; 44(11): 1745-1754
DOI: 10.1055/s-0031-1290824
DOI: 10.1055/s-0031-1290824
paper
O-Alkyl-N-acyl-N-phenylhydroxylamines as Photochemical Alkoxy Radical Precursors
Further Information
Publication History
Received: 21 December 2011
Accepted after revision: 09 March 2012
Publication Date:
10 May 2012 (online)
Dedicated to Professor Eluvathongal D. Jemmis on the occasion of his 60th birthday
Abstract
A simple and efficient technique for the photolysis of alkoxy radical precursors is developed. Irradiation of O-alkyl-N-acyl-N-phenylhydroxylamines, as representative alkoxy radical precursors, with ultraviolet light (≥254 nm) results in homolytic N–O bond cleavage to generate singlet alkoxy and acylaminyl caged radical pairs. These radicals, depending on the solvent employed, either escape from the cage to form fragmentation products, or undergo in-cage reactions to produce photorearrangement products. The homolytic cleavage of the N–O bond is analyzed using time-dependent density functional theory calculations. The nature of the N-acyl substituent on the O-alkyl-N-acyl-N-phenylhydroxylamines is shown to influence their ability to generate radicals. Furthermore, identification and trapping of the alkoxy radicals is demonstrated.
Key words
alkoxy radicals - O-alkyl-N-acyl-N-phenylhydroxylamines - homolytic cleavage - acylaminyl radical - alkoxy radical precursorsSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
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