O-Alkyl-N-acyl-N-phenylhydroxylamines as Photochemical Alkoxy Radical Precursors

Nilanjana Chowdhury; Anakuthil Anoop; N. D. Pradeep Singh

doi:10.1055/s-0031-1290824

Synthesis, Inhaltsverzeichnis

Synthesis 2012; 44(11): 1745-1754
DOI: 10.1055/s-0031-1290824

paper

O-Alkyl-N-acyl-N-phenylhydroxylamines as Photochemical Alkoxy Radical Precursors

Nilanjana Chowdhury

Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India, Fax: +91(3222)282252 eMail: ndpradeep@chem.iitkgp.ernet.in

,

Anakuthil Anoop*

Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India, Fax: +91(3222)282252 eMail: ndpradeep@chem.iitkgp.ernet.in

,

N. D. Pradeep Singh*

Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India, Fax: +91(3222)282252 eMail: ndpradeep@chem.iitkgp.ernet.in

› Institutsangaben

Abstract

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Dedicated to Professor Eluvathongal D. Jemmis on the occasion of his 60^th 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 precursors

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