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Des esters arylboroniques aux arylnitrones : synthèse d'esters arylboroniques et nouvelle réaction d'arylation de nitrones cycliques

Abstract : The first part is focused on the preparation of arylboronic esters derived from hexylene glycol, and bearing electron withdrawing substituents. We studied the palladium catalyzed borylation of electron-poor aryl halides with MPBH, an economic substitute for PinBH. MPBH, however, was found less efficient than PinBH. Next, a borylation through iodine/magnesium exchange with in situ trapping by the borate MPBOiPr was developed. This method allowed the borylation of aryl iodides carrying electron withdrawing and sensitive substituents, cleanly and safely (no accumulation of organomagnesium species), and scale up was possible (kilogram scale). Our attempts to use these arylboronic esters in addition reaction onto nitrones were unsuccessful. This led us to develop a new reaction: the direct arylation of cyclic nitrones with aryl halides. The coupling is dramatically accelerated by catalytic amounts of either a copper salt or pivalic acid. The reactions are fast and clean, and various (hetero)aryl iodides, bromides and chlorides can be used. Last, a mechanistic study allowed us to propose a mechanism for each additive.
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Emilien Demory. Des esters arylboroniques aux arylnitrones : synthèse d'esters arylboroniques et nouvelle réaction d'arylation de nitrones cycliques. Sciences agricoles. Université de Grenoble, 2012. Français. ⟨NNT : 2012GRENV053⟩. ⟨tel-00819878⟩

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