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Morita-baylis-hillman reactions between conjugated nitroalkenes or nitrodienes and carbonyl compounds

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Title Morita-baylis-hillman reactions between conjugated nitroalkenes or nitrodienes and carbonyl compounds
 
Creator DEB, I
SHANBHAG, P
MOBIN, SM
NAMBOOTHIRI, INN
 
Subject alkenes
alpha-hydroxyalkylation
c-c coupling
nitroalkenes
morita-baylis-hillman (mbh) reaction
synthetic methods
alpha-keto esters
functionalized 3-substituted 3-hydroxy-beta-lactams
remarkable rate acceleration
methyl vinyl ketone
dicarbonyl compounds
anticancer activity
activated alkenes
michael addition
nitroaliphatic compounds
synthetic applications
 
Description Morita-Baylis-Hillman (MBH) reactions between conjugated nitroalkenes or nitrodienes and various carbonyl compounds such as glyoxylate, trifluoropyruvate, pyruvaldehyde, oxomalonate, ninhydrin, and formaldehyde have been extensively investigated. The reactions proceeded smoothly in the presence of DMAP (40-100 mol-%) in acetonitrile and in some cases also in that of imidazole (100 mol-%) in CHCl(3) or THF, to provide the multifunctional adducts in good to excellent yields. The reactions catalyzed by DMAP in acetonitrile were superior to the imidazole-catalyzed reactions both in terms of the rate of reaction and in terms of the isolated yields of the MBH adducts. The catalytic roles played by DMAP and imidazole in these reactions, vis-a-vis other MBH catalysts such as DABCO, are attributed primarily to resonance stabilization of the initial zwitterionic intermediates. Whereas the E isomers are the major or exclusive products in the cases of glyoxylate, pyruvaldehyde, and formaldehyde, the Z isomers predominate in the cases of trifluoropyruvate and ninhydrin. Interestingly, oxomalonate forms E isomers with aromatic nitroalkenes and Z isomers with aliphatic ones. These selectivities and the formation of unusual deconjugated products in the case of certain beta-alkyl-nitroethylenes have been explained. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2011-10-12T11:19:38Z
2011-12-15T09:16:05Z
2011-10-12T11:19:38Z
2011-12-15T09:16:05Z
2009
 
Type Review
 
Identifier EUROPEAN JOURNAL OF ORGANIC CHEMISTRY,(24)4091-4101
1434-193X
http://dx.doi.org/10.1002/ejoc.200900475
http://dspace.library.iitb.ac.in/xmlui/handle/10054/13755
http://hdl.handle.net/100/2988
 
Language en