Uncommon 1,2-Migration of a Nitro Group Within a β-Nitrostyryl Moiety: Synthetic Scope and Mechanistic Details

The unusual migration of a nitro group from the β‐ to the α‐position of a β‐aryl‐α‐nitroethenyl moiety, following a nitrocyclopropane to isoxazoline N‐oxide isomerization, has been studied from a mechanistic and synthetic points of view. As a result, two series of isomeric isoxazoline N‐oxides could...

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Bibliographic Details
Published in:European journal of organic chemistry 2013-10, Vol.2013 (28), p.6298-6309
Main Authors: Bianchi, Lara, Ghelfi, Franco, Giorgi, Gianluca, Maccagno, Massimo, Petrillo, Giovanni, Spinelli, Domenico, Stenta, Marco, Tavani, Cinzia
Format: Article
Language:English
Subjects:
Alkenes
Heterocycles
Nitro group migration
Synthetic methods
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Summary:The unusual migration of a nitro group from the β‐ to the α‐position of a β‐aryl‐α‐nitroethenyl moiety, following a nitrocyclopropane to isoxazoline N‐oxide isomerization, has been studied from a mechanistic and synthetic points of view. As a result, two series of isomeric isoxazoline N‐oxides could be obtained under controlled conditions. When reacted with diazomethane, a model transposed isoxazoline cleanly furnished a new, interesting pyrazolylisoxazole. In spite of its infrequency, the migration of a nitro group from the β‐ to the α‐position of a β‐nitrostyryl moiety can be rationalized by stereo‐electronic factors, as shown here by means of computational and experimental studies. From the synthetic point a view, two series of isomeric isoxazoline N‐oxides can be obtained under controlled conditions.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201300856