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

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 19 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. (C) 2003 Elsevier Ltd. All rights reserved.