Peer-Reviewed Journal Details
Mandatory Fields
Heaney, F,Bourke, S,Cunningham, D,McArdle, P
1998
March
Journal Of The Chemical Society-Perkin Transactions 2
Steric control of reactivity: formation of oximes, benzodiazepinone N-oxides and isoxazoloquinolinones
Published
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Optional Fields
1,3-AZAPROTIO CYCLOTRANSFER POTENTIAL 1,3-DIPOLES ZH SYSTEMS NITRONES CYCLOADDITION GENERATION X=Y
547
559
Reaction of the alkenyl carbonyl compounds 1 with hydroxylamine can lead to the formation of the oximes 2, the benzodiazepinone N-oxides 3 or the isoxazoloquinolinones 5. The product(s) of reaction are shown to depend on the electronic nature of the terminal olefinic substituent R-3 and the space filling capacity of the substituents R-1, R-2 and R-4. When the olefinic centre is electron poor (R-3 = CO2Et) ketocarbonyls convert exclusively to bicyclic nitrones 3 whereas aldehydes are more sensitive to subtle changes in skeletal structure and give rise to oximes 2, tricycles 5 or mixtures of both, For aldehyde and ketone substrates when the olefinic centre carries an aryl substituent (R-3 = Ph) the primary product of reaction is the corresponding oxime which on thermal activation converts to the tricyclic isoxazoloquinolinones.
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