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Synthesis 2010(2): 343-348  
DOI: 10.1055/s-0029-1217109
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Intramolecular 1,3-Dipolar Cycloaddition of Alkenylnitrones of the 4H-Imidazole Series: Synthesis of a New Nitroxide pH-Sensitive Spin Probe

Denis A. Morozov*a,b, Igor A. Kirilyuka, Yuri V. Gatilova, Irina Yu. Bagryanskayaa, Julya Yu. Bozhkoc, Denis A. Komarovc, Igor A. Grigor’eva
a Novosibirsk Institute of Organic Chemistry SB RAS, ave. akad. Lavrentjeva 9, Novosibirsk 630090, Russian Federation
b Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
Fax: +7(383)3309752; e-Mail: m_falcon@nioch.nsc.ru;
c Institute of Chemical Kinetics and Combustion SB RAS, Institutskaya 3, Novosibirsk 630090, Russian Federation
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Publikationsverlauf

Received 11 August 2009
Publikationsdatum:
06. November 2009 (online)

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Abstract

A new method was used for the preparation of a pH-sensitive spin probe involving an intramolecular 1,3-dipolar cycloaddition - reductive isoxazolidine ring-opening - oxidation reaction sequence. 2-(2-Allyloxyphenyl)-5-R-4,4-dimethyl-4H-imidazole-3-oxides (R = Me, NMe2), prepared from 3-hydroxylamino-3-methylbutan-2-one, undergo intramolecular 1,3-dipolar cycloaddition upon heating in toluene. Treatment of the cycloadducts with low-valence titanium (LVT) reagent resulted in reductive cleavage of the N-O bond of the isoxazolidine ring to give 3′-hydroxymethyl-5,5-dimethyl-4-R-2,5-dihydrospiro[imidazol-2,4′-chromane]s. The amine (R = NMe2) was then oxidized with MCPBA to the target nitroxide - 3′-hydroxymethyl-5,5-dimethyl-4-dimethylamino-2,5-dihydrospiro[imidazole-2,4′-chroman]-1-oxyl.

Key words

1,3-dipolar cycloaddition - low-valence titanium - nitroxide radical - 4H-imidazole 3-oxide - pH-sensitive spin probe

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CCDC-742584 (10b) and CCDC-742583 (1) contain all the crystallographic details for this publication. These are available free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or can be ordered from the following address: Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK; Fax: +44(1223)336033, or deposit@ccdc.cam.ac.uk.