La fonctionnalisation par voie catalytique de substrats naturels a été menée dans le but d’accroître l’activité biologique reconnue de la molécule naturelle de départ ou de découvrir de nouvelles activités. Des réactions catalytiques telles que l’hydroformylation et l’alcoxycarbonylation mettant en jeu le monoxyde de carbone et catalysées par des complexes du rhodium et du palladium ou encore la réaction de cycloisomérisation catalysée par des complexes d’or ou du platine ont déjà permis d’accéder sélectivement à de nouvelles molécules intéressantes. Dans une première partie nous nous sommes intéressés à l’huile essentielle du cèdre de l’atlas (cedrus atlantica) qui est constituée d’une partie hydrocarbure et d’une partie oxygénée. Notre étude s’est focalisée sur la partie oxygénée de l’huile essentielle du cèdre de l’atlas qui est composée de deux cétones isomères, les Z- et E-α- atlantones. La réaction de cyclocarbonylation des alcools allyliques dérivés des α-atlantones a été étudiée. Cette réaction catalysée par des complexes du palladium permet d’obtenir des lactones à 5 et à 6 chainons. Plusieurs systèmes catalytiques de type [PdCl2L2]/SnCl2.2H2O ont été testés, lors de cette étude et nous avons montré que la regiosélectivité de la réaction peut être contrôlée par la nature du ligand utilisé. Ainsi, les ligands monophosphines favorisent la formation des lactones à 6 chainons obtenues sous forme de deux diastéréoisomères et les ligands diphosphines favorisent la formation de celles à 5 chainons obtenues sous forme de quatre diastéréoisomères. Ces lactones sont complètement caractérisées par RMN 1D et 2D et la spectrométrie de masse. Des monocristaux ont été obtenus et analysés par diffraction des rayons X. Dans une deuxième partie, la synthèse d’aldéhydes par réaction d’hydroformylation à partir de l’estragol, un allylbenzène extrait de l’huile essentielle de l’estragon, a été étudiée en présence du système catalytique [Rh(cod)(OMe)]2/ligand phosphole. Ainsi, nous avons évalué l’activité de plusieurs ligands phospholes dans cette réaction d’hydroformylation. Tous les ligands phospholes testés se sont révélés actifs et chimiosélectifs dans la réaction d’hydroformylation d’estragol pour donner majoritairement l’aldéhyde linéaire correspondant. Dans une étude préliminaire, nous avons étudié la réaction de cycloisomérisation d’énynes oxygénés dérivés d’α-atlantones catalysée par des complexes d’or ou du platine. / The catalytic functionnalisation of the natural substrates have been developped to increase their own biological activity or to give them new biological properties. The reactions such as hydroformylation, alkoxycarbonylation and cyclocarbonylation in presence of carbon monoxide catalyzed by rhodium or palladium complexes or cycloisomerisation catalyzed by gold or platinium complexes give an access to new interesting molecules with high selectivity. In first part we have been interested in study of the essential oil of the Atlas Cedar (Cedrus Atlantica). We focused in this study on the oxygenated fraction, which contains the two sesquiterpenic ketone,isomers Z- and E-α-atlantone. Starting from allylic alcohols derived from α-atlantone, the cyclocarbonylation reaction catalyzed by palladium complexes have been investigated. This reaction provide a mixture of five and six membered ring lactones with excellent conversion and excellent chemioselectivity. Different catalytic systems [PdCl2L2]/SnCl2.2H2O or [Pd(OAc)2]/L have been studied. The regiochemical control depends on the nature of the ligand L. The monophosphine ligands favor the formation of the six-membered ring lactones obtained as two diastereomers, while the diphosphine ligands allow the formation of the five- membered ring lactone obtained as four diastereomers. These new lactones were fully characterized by 1D and 2D NMR and mass spectrometry. Monocrystals of the six- and five-membered ring lactones suitable for X-ray diffraction analysis have been obtained. In a second part the hydroformylation reaction of estragol, a natural allylbenzene extracted from the essential oil of estragon, have been studied with the catalytic system [Rh(cod)(OMe)]2/phospholes. All the phosphole ligands show good activities and chemoselectivities in the hydroformylation of estragol and affords the linear aldehyde corresponding as a major product. In a preliminary study, we have investigated the cycloisomerisation reaction of o-tethered enynes derived from α-atlantones catalyzed by gold or platinum complexes.

Palynology, the study of organic microfossils, is an important tool for improving our understanding of past environments and landscapes. Palynology provides a wealth of information from which climatic and environmental conditions can be inferred. However, inferred climatic and environmental conditions are often open to interpretation. Assumptions made about past climate conditions from pollen assemblages often rely on qualitative understanding of modern-day vegetation distributions, rather than empirical relationships. Historic anthropogenic impact on the environment must also be inferred, and assessments made as to whether vegetation changes are a result of climate change or human impact. This study seeks to address some of the questions that arise through the interpretation of pollen assemblages, by establishing empirical relationships between the geochemistry of modern pollen and climate or environmental controls. It focuses on the pollen of the climatically sensitive montane conifer Cedrus atlantica, which is distributed across the mountains of Morocco and Algeria. The study investigates aspects of modern pollen geochemistry and morphology and finds a strong relationship between the stable carbon isotope composition of modern pollen and mean annual precipitation (r2 = 0.54, p <0.001) and summer precipitation (r2 = 0.63, p <0.0001). Furthermore, a stronger relationship exists with aridity measured using the self-calibrating Palmer Drought Severity Index (r2 = 0.86, p <0.0001), suggesting that the stable carbon isotope composition of Cedrus atlantica pollen is influenced by environmental moisture availability. The study also finds there is an increased abundance of ultraviolet absorbing compounds (UACs) in modern Cedrus atlantica pollen with increasing summer UV-B flux. This relationship was evident with samples growing in their native range (r2 = 0.84, p <0.0001), but not with samples from outside this range (r2 = 0.00, p = 0.99), suggesting a possible genetic influence. Lastly, the study finds that grain size of Cedrus atlantica pollen is highly variable within and between samples, and we rule out climatic control on pollen grain size. These results suggest that quantitative relationships can be established between the geochemistry of Cedrus atlantica pollen and environmental and climatic influences. Stable carbon isotope analysis of fossil pollen could be used as a proxy for reconstruction of summer moisture availability, while analysis of UACs in fossil pollen could be used as a proxy for the reconstruction of summer UV-B flux. These proxies will enhance our understanding of climatic and environmental change in Northwest Africa and will complement existing palynological techniques for environmental and climate reconstruction. Palynology, the study of organic microfossils, is an important tool for improving our understanding of past environments and landscapes. Palynology provides a wealth of information from which climatic and environmental conditions can be inferred. However, inferred climatic and environmental conditions are often open to interpretation. Assumptions made about past climate conditions from pollen assemblages often rely on qualitative understanding of modern-day vegetation distributions, rather than empirical relationships. Historic anthropogenic impact on the environment must also be inferred, and assessments made as to whether vegetation changes are a result of climate change or human impact. This study seeks to address some of the questions that arise through the interpretation of pollen assemblages, by establishing empirical relationships between the geochemistry of modern pollen and climate or environmental controls. It focuses on the pollen of the climatically sensitive montane conifer Cedrus atlantica, which is distributed across the mountains of Morocco and Algeria. The study investigates aspects of modern pollen geochemistry and morphology and finds a strong relationship between the stable carbon isotope composition of modern pollen and mean annual precipitation (r2 = 0.54, p <0.001) and summer precipitation (r2 = 0.63, p <0.0001). Furthermore, a stronger relationship exists with aridity measured using the self-calibrating Palmer Drought Severity Index (r2 = 0.86, p <0.0001), suggesting that the stable carbon isotope composition of Cedrus atlantica pollen is influenced by environmental moisture availability. The study also finds there is an increased abundance of ultraviolet absorbing compounds (UACs) in modern Cedrus atlantica pollen with increasing summer UV-B flux. This relationship was evident with samples growing in their native range (r2 = 0.84, p <0.0001), but not with samples from outside this range (r2 = 0.00, p = 0.99), suggesting a possible genetic influence. Lastly, the study finds that grain size of Cedrus atlantica pollen is highly variable within and between samples, and we rule out climatic control on pollen grain size. These results suggest that quantitative relationships can be established between the geochemistry of Cedrus atlantica pollen and environmental and climatic influences. Stable carbon isotope analysis of fossil pollen could be used as a proxy for reconstruction of summer moisture availability, while analysis of UACs in fossil pollen could be used as a proxy for the reconstruction of summer UV-B flux. These proxies will enhance our understanding of climatic and environmental change in Northwest Africa and will complement existing palynological techniques for environmental and climate reconstruction.