Selectivities in the 1,3-dipolar cycloaddition of nitrile oxides to dicyclopentadiene and its derivatives |
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Authors: | Irishi NN Namboothiri Namrata Rastogi Shaikh M Mobin |
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Institution: | a Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076, India b Analytical Science Division, Central Salt and Marine Chemicals Research Institute, Bhavnagar Gujarat 364 002, India c National Single Crystal X-ray Diffraction Facility, Indian Institute of Technology, Bombay, Mumbai 400 076, India d Department of Chemistry, Bar-Ilan University, Ramat Gan 52900, Israel |
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Abstract: | 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 cycloaddition 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. |
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Keywords: | Nitrile oxide 1 3-Dipolar cycloaddition Dicyclopentadiene Thiele's ester |
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