STEREOSELECTIVITY AND REGIOSELECTIVITY
IN ORGANIC CHEMISTRY: NOVEL SYSTEMS AND
APPLICATIONS
Résumé
Molecular recognition has become a very important field of research in chemistry during the last decades. This
chemical phenomenon is responsible for all processes occurring in biology and asymmetric synthesis is based
upon the capability of molecules or substrates to recognise each other in a selective manner. In this thesis, the
design, preparation and evaluation of a series of new synthetic receptors has been described. The importance of
regioselectivity and stereoselectivity in molecular recognition has also been underlined with two different
biological examples.
The capability of host molecules, derived from (+)-tartaric acid, to accommodate various guests in a selective
manner was demonstrated using 1H-NMR spectroscopy (paper I). These host molecules, known as TADDOLs,
enantioselectively recognised the valuable chiral alcohols glycidol and menthol. Macromolecular receptors, i.e.
molecularly imprinted polymers (MIPs), were also prepared in order to catalyse the aldol reaction between either
(R)- or (S)-camphor and benzaldehyde (paper II). With the help of analytical methods, it was demonstrated that
the MIPs interacted in a selective manner with the enantiomers of camphor. Moreover, these MIPs enhanced
significantly the rate of the aldol condensation mentioned above.
Regarding biological systems, various regioisomeric analogues of benzoic acid have been tested as antifeedants
against the pine weevil Hylobius abietis (paper III and IV). The regioisomers studied displayed very different
antifeedant activities. The significance of stereoisomerism on pheromone function has been shown in the
preparation of lures for the control of the insect pest Argyrotaenia sphaleropa (paper V). It was demonstrated that
male leafrollers could be caught by a lure containing components of the female sex pheromone gland.
chemical phenomenon is responsible for all processes occurring in biology and asymmetric synthesis is based
upon the capability of molecules or substrates to recognise each other in a selective manner. In this thesis, the
design, preparation and evaluation of a series of new synthetic receptors has been described. The importance of
regioselectivity and stereoselectivity in molecular recognition has also been underlined with two different
biological examples.
The capability of host molecules, derived from (+)-tartaric acid, to accommodate various guests in a selective
manner was demonstrated using 1H-NMR spectroscopy (paper I). These host molecules, known as TADDOLs,
enantioselectively recognised the valuable chiral alcohols glycidol and menthol. Macromolecular receptors, i.e.
molecularly imprinted polymers (MIPs), were also prepared in order to catalyse the aldol reaction between either
(R)- or (S)-camphor and benzaldehyde (paper II). With the help of analytical methods, it was demonstrated that
the MIPs interacted in a selective manner with the enantiomers of camphor. Moreover, these MIPs enhanced
significantly the rate of the aldol condensation mentioned above.
Regarding biological systems, various regioisomeric analogues of benzoic acid have been tested as antifeedants
against the pine weevil Hylobius abietis (paper III and IV). The regioisomers studied displayed very different
antifeedant activities. The significance of stereoisomerism on pheromone function has been shown in the
preparation of lures for the control of the insect pest Argyrotaenia sphaleropa (paper V). It was demonstrated that
male leafrollers could be caught by a lure containing components of the female sex pheromone gland.