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Selectivities in the 1,3-dipolar cycloaddition of nitrile oxides to dicyclopentadiene and its derivatives

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Title Selectivities in the 1,3-dipolar cycloaddition of nitrile oxides to dicyclopentadiene and its derivatives
 
Creator NAMBOOTHIRI, IRISHI NN
RASTOGI, NAMRATA
GANGULY, BISHWAJIT
SHAIKH, MOBIN M
COJOCARU, MIRIAM
 
Subject cycloaddition
computational methods
derivatives
 
Description The 1,3-dipolar cycloaddition of nitrile oxides, generated from aldoximes and nitroalkanes, to dicyclopentadiene proceeds with complete chemo- and stereoselectivity. The approach of the dipole takes place exclusively from the exo-face of the bicycloheptane moiety providing a mixture of regioisomers in approximately 55:45 ratio. On the other hand, nitrile oxide cloaddition to dimethyldicyclopentadiene dicarboxylate (Thiele’s ester), besides exhibiting chemo- and stereoselectivity as in the case of dicyclopentadiene, exhibits complete
regioselectivity as well providing a single isomer in good yield. The Influence of remote substituents, including sterically ‘sterile’ ones, on
the regioselectivity has also been investigated using 8-hydroxy and 1-keto derivatives of dicyclopentadiene. These experimental observations have been investigated through gas phase and solvent model MO calculations on the transition state geometries at semiempirical (PM3) and
hybrid ab initio-DFT levels of theory. The Computational methods employed in this study were rigorously tested by performing model
calculations on well-established experimental observations.
Copyright to Elsevier
CSIR (India), IIT Bombay,
 
Publisher Elsevier
 
Date 2008-11-04T08:57:23Z
2011-11-25T12:19:42Z
2011-12-26T13:06:43Z
2011-12-27T05:54:43Z
2008-11-04T08:57:23Z
2011-11-25T12:19:42Z
2011-12-26T13:06:43Z
2011-12-27T05:54:43Z
2003
 
Type Article
 
Identifier Tetrahedron 60, 1453-1462
0040-4020
http://dx.doi.org/10.1016/j.tet.2003.12.026
http://hdl.handle.net/10054/63
http://dspace.library.iitb.ac.in/xmlui/handle/10054/63
 
Language en