A theoretical evaluation of the Michael-Acceptor ability of conjugated nitroalkenes
DSpace at IIT Bombay
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Title |
A theoretical evaluation of the Michael-Acceptor ability of conjugated nitroalkenes
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Creator |
RAI, VISHAL
NAMBOOTHIRI, IRISHI NN |
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Subject |
natural bond orbital
ab initio calculations density functional theory |
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Description |
A theoretical evaluation of the relative Michael-acceptor abilities of a variety of substituted aromatic and aliphatic nitroalkenes is reported. Several global and local reactivity indices were evaluated with the incorporation of natural charge obtained from natural bond orbital (NBO) analysis. Natural charges at the carbon atom β to the NO2 group and the condensed Fukui functions derived by this method were quite consistent with the reactivity. The reactivity of nitroalkenes was further examined by kinetic experiments that were monitored by NMR spectroscopy. The isolated yields reported in the literature were also found to have a dependable correlation with these reactivity indices in the majority of cases. The computational methods employed in the calculation of natural charge, the condensed Fukui function, local softness and other reactivity parameters were chosen after evaluation of various methods for their ability to satisfactorily predict the NMR chemical shift of the 1H atom β and cis to the NO2 group (β-H) in nitroalkenes. Our approach appears suitable for predicting the relative Michael-acceptor abilities of various nitroalkenes, based on the β-carbon natural charge and the indices derived from it. Copyright Wiley-VCH Verlag GmbH & Co. KGaA |
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Date |
2008-11-05T11:15:44Z
2011-11-25T12:19:42Z 2011-12-26T13:05:12Z 2011-12-27T05:51:25Z 2008-11-05T11:15:44Z 2011-11-25T12:19:42Z 2011-12-26T13:05:12Z 2011-12-27T05:51:25Z 2006 |
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Type |
Article
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Identifier |
Eur. J. Org. Chem. 2006, 4693–4703
1434-193X (print) http://dx.doi.org/10.1002/ejoc.200600505 http://hdl.handle.net/10054/64 http://dspace.library.iitb.ac.in/xmlui/handle/10054/64 |
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Language |
en
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Rights |
Copyright Wiley-VCH Verlag GmbH & Co. KGaA
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