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STEREOSELECTIVITY and REGIOSELECTIVITYIN ORGANIC CHEMISTRY: NOVEL SYSTEMS ANDAPPLICATIONS Sacha Legrand

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STEREOSELECTIVITY and REGIOSELECTIVITYIN ORGANIC CHEMISTRY: NOVEL SYSTEMS ANDAPPLICATIONS Sacha Legrand STEREOSELECTIVITY AND REGIOSELECTIVITYIN ORGANIC CHEMISTRY: NOVEL SYSTEMS ANDAPPLICATIONS Sacha Legrand To cite this version: Sacha Legrand. STEREOSELECTIVITY AND REGIOSELECTIVITYIN ORGANIC CHEMISTRY: NOVEL SYSTEMS ANDAPPLICATIONS. Other. University of Kalmar, 2006. English. tel- 00080096 HAL Id: tel-00080096 https://tel.archives-ouvertes.fr/tel-00080096 Submitted on 14 Jun 2006 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. STEREOSELECTIVITY AND REGIOSELECTIVITY IN ORGANIC CHEMISTRY: NOVEL SYSTEMS AND APPLICATIONS Sacha Legrand Ingénieur Chimiste de l’Institut National des Sciences Appliquées (INSA) de Rouen (France). Doctoral Thesis Kalmar 2006 Department of Chemistry and Biomedical Sciences University of Kalmar Sweden Akademisk avhandling som, för vinnande av doktorexamen i organisk kemi vid fakulteten för naturvetenskap och teknik vid Högskolan i Kalmar, kommer att offentligen försvaras i Falkens hörsal, Nygatan 18b, Kalmar, torsdagen den 2 mars kl 09.00. Opponent: Dr Tina Persson, Department of Organic Chemistry 1, Lund University, Lund, Sweden. 1 Organisation Document name University of Kalmar DOCTORAL DISSERTATION Department of Chemistry and Biomedical Sciences Date of issue SE-391 82 Kalmar, Sweden 26.01.2006 Sponsoring organisation Author: Sacha Legrand University of Kalmar, Sweden Title and subtitle: Stereoselectivity and regioselectivity in organic chemistry: novel systems and applications Abstract 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. Key words: aldol reaction, Argyrotaenia sphaleropa, Hylobius abietis, methyl benzoic esters, molecularly imprinted polymer, molecular recognition, NMR, pheromones, regioselectivity, stereoselectivity, TADDOL. Classification system and/or index terms (if any) Supplementary bibliographical information Language: English ISSN and key title: 1650-2779 ISBN: 91-89584-57-0 Recipient’s notes Number of pages Price 155 Security classification Distribution by (name and address) Sacha Legrand, Department of Chemistry and Biomedical Sciences, University of Kalmar, Kalmar, Sweden I, the undersigned, being the copyright owner of the abstract of the above-mentioned dissertation, hereby grant to all reference sources to publish and disseminate the abstract of the above-mentioned dissertation. Signature Date 26.01.2006 2 Kirsille, Pour Maman, Papa et Lara “Carpe Diem Quam Minimum Credula Postero” Quitus Horatius Flaccus, liv. I, ode XI, v. 8. Copyright © Sacha Legrand, Kalmar 2006. 3 Abstract 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. Keywords: aldol reaction, Argyrotaenia sphaleropa, Hylobius abietis, methyl benzoic esters, molecularly imprinted polymer, molecular recognition, NMR, pheromones, regioselectivity, stereoselectivity, TADDOL. Sacha Legrand; Stereoselectivity and Regioselectivity in Organic Chemistry: Novel Systems and Applications. Department of Chemistry and Biomedical Sciences, University of Kalmar, Kalmar (Sweden). ISBN: 91-89584-57-0. 4 List of Publications The thesis is based on the following papers. They are referred to by their roman numerals in the text. I. Legrand, S.; Luukinen, H.; Isaksson, R.; Kilpeläinen, I.; Lindström, M.; Nicholls, I.A.; Unelius, C.R. Synthesis, NMR conformational studies and host-guest behaviour of new (+)-tartaric acid derivatives. Tetrahedron: Asymmetry, 2005, 16, 635-640. II. Hedin-Dahlström, J.; Rosengren-Holmberg, J.; Legrand, S.; Wikman, S.; Nicholls, I.A. A synthetic class II aldolase mimic. Submitted (2006). III. Legrand, S.; Nordlander, G.; Nordenhem, H.; Borg-Karlson, A.-K.; Unelius, C.R. Hydroxy-methoxybenzoic methyl esters: synthesis and antifeedant activity on the pine weevil, Hylobius abietis. Zeitschrift für Naturforschung B, 2004, 59, 829-835. IV. Unelius, C.R.; Nordlander, G.; Nordenhem, H.; Hellqvist, C.; Legrand, S.; Borg- Karlson, A.K. Structure-activity relationships of benzoic acid derivatives as antifeedants for the pine weevil Hylobius abietis. Accepted for publication in Journal of Chemical Ecology. V. Legrand, S.; Botton, M.; Coracini, M.; Wiztgall, P.; Unelius, C.R. Synthesis and field tests of sex pheromone components of the leafroller Argyrotaenia sphaleropa. Zeitschrift für Naturforschung C, 2004, 59, 708-712. Additional work outside the scope of this thesis: El-Sayed, A.M.; Delisle, J.; De Lury, N.; Gut, L.J.; Judd, G.J.R.; Legrand, S.; Reissig, W.H.; Roelofs, W.L.; Unelius, C.R.; Trimble, R.M. Geographic variation in pheromone chemistry, antennal electrophysiology, and pheromone-mediated trap catch of north American populations of the Obliquanted Leafroller. Environmental Entomology, 2003, 32, 471-476. The published papers are reprinted with the kind permission of Elsevier Science (I), the American Chemical Society (II), Verlag der Zeitschrift für Naturforschung (III and V), and Springer Science and Business Media (IV). 5 ABBREVIATIONS ABCC 1,1’-Azobis(cyclohexanecarbonitrile) ABDV 2,2’-Azobis(2,4-dimethylvaleronitrile) Ac Acetyl AGP α-Acid glycoprotein AIBN Azobis(isobutyronitrile) app. Kd Apparent dissociation constant Ar Aromatic BET Nitrogen adsorption isotherm measurements BINOL 1,1’-Bi-2-naphthol Bn Benzyl Boc t-Butoxycarbonyl Bu Butyl Cbz Carbobenzyloxy CD Cyclodextrin CDK Cyclin dependent kinase COSY Correlated spectroscopy CSP Chiral stationary phase DATD N,N’-Diallyl-L-tartardiamide DCC Dicyclohexylcarbodiimide DEPT Distortionless enhancement by polarization transfer DMAP Dimethylaminopyridine DMB 3,5-Dimethylbenzoate DME Ethylene glycol dimethyl ether DMF Dimethylformamide DMSO Dimethyl sulfoxide
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