Positron Emission Tomography (PET) has great value in research and clinical applications from oncology to neurodegenerative disorders. However, there is a barrier in translating biological knowledge into new PET applications due in part to the lack of efficient, widely applicable methods for labelling compounds with PET radioisotopes. Herein, a generic approach to radiolabelling is presented which is direct, broadly applicable and potentially adaptable to either of the two most commonly used PET radioisotopes, 11C and 18F. This approach employs the advantages of solid phase synthesis to achieve selective release of only the desired radiolabelled product from a solid support in a single step, simplifying purification and hence improving synthetic efficiency. Polystyrene resin was functionalised with a 1,2-diol group; this allowed the covalent attachment of compounds bearing boronic acid groups via formation of a boronate ester linkage. A Suzuki-Miyaura reaction with methyl iodide was used to cleave a model compound from the resin in 61% conversion after five minutes. This reaction was adapted to develop a fully automated radiosynthesis with [11C]- methyl iodide which generated a radiolabelled model compound in 2 – 7% non-decay-corrected radiochemical yield. This provided proof of concept for the simultaneous cleavage of compounds from the resin and radiolabelling with 11C. A boronic acid precursor of the known radiotracer [11C]-M-MTEB was attached to the resin and successfully radiolabelled with 11C in 2.4% non-decay-corrected radiochemical yield and 96 – 100% radiochemical purity under the same conditions. Furthermore, the potential adaptability of this solid phase approach to 18F radiolabelling was demonstrated by treatment of the resin-bound small molecules and peptides with potassium bifluoride, which released the compounds rapidly as trifluoroborate salts.

Ce travail a tout d’abord porté sur la réactivité des dérivés borés puis sur la réaction de O-alkylation des alcools aromatiques. L’utilisation des composés borés est en plein essor. Ils sont employés comme partenaires de couplage dans la réaction de Suzuki et les réactions d’additions [1,4] catalysées au rhodium pour la synthèse de molécules à hautes valeurs ajoutées. La polarisation de la liaison C-B induit le caractère nucléophile de ces composés. Cette réactivité a été exploitée pour la formation de liaisons C-F par fluoration électrophile. L’utilisation de Selectfluor® comme agent de fluoration aboutit à de bons rendements. Toutefois, la nucléophilie des composés alkylborés peut être inversée par substitution nucléophile oxydante. Ainsi, une méthode créant des liaisons C-N a pu être développée et a permis la synthèse d’amides à partir de nitriles et de sels de trifluoroborates de potassium en présence de Cu(OAc)2 et BF3.OEt2. En vue de l’importance de la chimie des éthers en synthèse organique, une méthode de préparation d’éthers aryliques a été développée au laboratoire. En partant d’un système stœchiométrique en trifluorure de bore, un système catalytique impliquant du triflate de cérium a été mis au point. Afin de répondre au mieux au concept de la chimie verte, un système catalytique hétérogène, sans solvant, a été décrit. Dans ce cas, le catalyseur employé est le Nafion® NR50, facilement recyclable, sans perte d’activité, et conduisant à de bons rendements avec les alcools aliphatiques et aromatiques. Des amines aromatiques secondaires peuvent également être préparées par cette méthode / This thesis describes the study of the reactivity of boron compounds and the O-alkylation of aromatic alcohols. The use of boronic derivatives increased considerably over the past decades. There are used as cross-coupling partners in the Suzuki reaction and for 1,4 rhodium-catalyzed addition reaction. The nucleophilic nature of these compounds was induced by the C-B bond polarization. This peculiar reactivity was studied for the C-F bond formation. The use of Selectfluor® as fluorinating agent leads to good yields. Nevertheless, the polarity of the C-B bond could be reversed by oxidative nucleophilic substitution. Thus, C–N bond could be formed from nitriles and potassium trifluoroborate salts promoted by Cu(OAc)2 in the presence of BF3.OEt2. Due to the importance of ether chemistry in organic synthesis, the O-alkylation of phenol derivatives was achieved in the laboratory. From a stoichiometric amount of Lewis acid, BF3.OEt2, a catalytic system was developed involving cerium triflate. Then, the focus on green chemistry led to use a heterogeneous catalyst. Where Nafion® NR50 appears as a suitable catalyst for the ether synthesis