Résumé : Le processus de règlement des litiges par la voie de l’arbitrage a nourri des ambitions économiques énormes dans les sphères juridiques où ce mécanisme a été instauré. L’efficacité de ce processus qui signifie entre autre un processus ayant abouti à une application, voire une exécution effective des protagonistes est un gage de la réalisation de ces ambitions. Or, ce processus peut être compromis du fait de l’annulation de la sentence arbitrale par un juge dont l’intervention dans le processus peut soit le renforcer, soit l’annihiler fondamentalement. Cette situation explique dans une large mesure les raisons pour lesquelles la doctrine juridique se place en faveur d’une collaboration solide entre la justice publique et la justice privée de l’arbitrage. Comment cette question de l’annulation de la sentence arbitrale est abordée dans les sphères juridiques du Québec et de l’Ohada? Quels sont les effets juridiques issus de la comparaison de cette situation dans chacune de ces sphères? Telle se présente la substance de cette recherche dont la méthode comparative est alimentée par le paradigme de l’herméneutique juridique et son corollaire le pluralisme juridique. Les résultats issus du dialogue comparatif devraient participer à une amélioration des situations problématiques décelées dans les sphères concernées. // Abstract : The rule process of lawsuits based on arbitration has filled out huge economic ambitions related to judicial spheres where this mechanism has been established. The efficiency of this process, which among others, has led to an application, indeed a real execution of the protagonists, is somewhat a guarantee to the fulfilment of these ambitions. However, this process can be compromised because of the cancellation of the arbitral sentence by a judge whose intervention in the process can either reinforce it or destroy it. This situation mainly explains the reasons why the juridical doctrine is in favour of a solid collaboration. How do the juridical sphere of Quebec and Ohada tackle this issue of the cancellation of the arbitral sentence? What are the juridical effects stemmed from the comparism of this situation in both spheres? The way the substance of this research appears and whose comparative method is fed by the paradigm of the juridical hermeneutics and its juridical pluralism corollary. The results stemmed from the comparative dialog should participate in improving problematic situations detected in the applied spheres.

Th. doct.--Droit--Paris 1, 2000. / Bibliogr. p. 1009-1033. Index.

Catalyst-Controlled Divergent C–H Functionalization of Unsymmetrical 2-Aryl Cyclic 1,3-Dicarbonyl Compounds with Alkynes and Alkenes A problem faced within the area of C–H functionalization is achieving siteselectivity when several similar C–H bonds are present within a given compound. One solution to this problem is the development of reactions that employ different catalytic systems to control the required selectivity. Herein, it is shown that such catalyst-controlled selectivity could be achieved on 2-aryl cyclic 1,3-dicarbonyl compounds where there exist two potential, non-adjacent sites for C–H functionalization. Examples demonstrate the palladium- and ruthenium-catalysed oxidative annulations of the 2-aryl cyclic 1,3-dicarbonyl substrates with alkynes, as well as with alkenes, where initial C–H bond cleavage occurs at one of two potential sites, depending on the catalyst used, which give unique products. 1,4-Rhodium(III) Migration in the One-Carbon Oxidative Annulations of 2-Arylphenols, Benzamides, and Benzoic Acids with 1,3-Enynes Oxidative annulations of 2-arylphenols, benzamides, and benzoic acids with alkynes and enynes are precedented and provide a range of heterocyclic products. However, in these examples, either the alkyne or enyne acts as a two-carbon annulation partner, reacting only across the alkynyl moiety. Herein, a more expansive scope of a previously published process in which 1,3-enynes, possessing allylic hydrogen atoms cis to the alkyne, undergo oxidative annulations with the three aforementioned classes of substrates as a one-carbon annulation partner is described. Proposed to occur via the 1,4-migration of a rhodium(III) species, annulated products were formed from a range of 1,3-enynes and substrates possessing a variety of functional groups.

We have developed an one-pot reaction procedure to polysubstituted pyroglutamates with three contiguous chiral centers. The results were applied to the synthetic studies toward kainic acid and lycorane.

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Cuban and Brazilian red bee propolis (CRP and BRP), a waxy red substance made by bees and found on the outside of beehives, has been used for thousands of years in folk medicine to treat a wide range of ailments. Hundreds of compounds have been isolated from CRP and BRP, however, very little is known about the individual components and their contributions to the biological activity of the propolis as a whole. Of the compounds isolated, many are simple isoflavans, complex isoflavanoids, or dimeric isoflavanoids. Herein, we report the total syntheses of isoflavanoid natural products isolated from Cuban and Brazilian red bee propolis: neovestitol, retusapurpurin A, and retusapurpurin B, as well efforts towards the total synthesis of the dimeric isoflavanoid propolone B. The synthetic strategies described will allow for biological testing on these natural products, as well unnatural analogs. Neovestitol, a simple isoflavan, has displayed interesting anti-inflammatory activity in mice. However, to the best of our knowledge, no syntheses of the natural product have been reported. Herein, we report the development of a [4 + 2] cycloaddition to access the neovestitol core. Furthermore, we developed a dynamic acylative kinetic resolution that led to the synthesis of enantiopure (S)-neovestitol. The asymmetric synthesis allowed for confirmation of the absolute stereochemistry of the isolated natural product, which had previously only been assigned based on analogy with related isoflavans. Retusapurpurins A and B are complex isoflavanoids that are often attributed with giving red bee propolis a red color. Additionally, these compounds contain a neovestitol subunit. In this thesis, we describe the development of a novel annulation promoted by bis(trifluoromethane)sulfonimide that enabled us to construct the retusapurpurin core. This methodology was used to synthesize a small library of unnatural retusapurpurin analogs. More recently, a new class of dimeric isoflavanoids were reported, propolones A-D, propolonones A-C, and propolol A. Of the eight compounds, propolones A-C and propolonones A and B contain a neovestitol subunit. Herein, we describe our efforts towards using a platinum(II)-catalyzed migratory cycloisomerization that would allow for access to these eight natural products, as well as unnatural analogs. / 2025-09-18T00:00:00Z

Reaction of 3-sulfonyl acetamides with various substituted methyl acrylate derivatives furnished pyroglutamate and glutarimidess via [3+2] and [3+3] cycloaddition respectively. The results were applied to the synthesis of pyrrolizidine skeleton, tylophorine, cryptopleurine and fused bicyclic glutarimides.

We use stepwise [3+3] annulation to prepare the asymmetric glutarimides, and then we can build substituent group in C6 position after choosing regioselective addition reaction. And we establish a new approach to benzo[h]quinoline skeleton starting from glutarimides via ring-closing reaction. Finally, we applied this method to the synthetic studies toward benzo[h]quinoline derivatives.

Despite progress in the metal-catalyzed synthesis of aromatic heterocycles, annulation routes towards 6-membered heterocycles remain underdeveloped. Specifically, routes towards pyridines are rare in spite of the prevalence of this moiety in novel drug candidates. Our initial efforts towards pyridines featured oximes as competent nucleophiles in the intramolecular, 6-exo dig annulation of alkynes using Brønsted acid catalysis. Two of the oxidation states required for subsequent aromatization are contained within the oxime via loss of water. An extension of this chemistry is presented and discussed, and involves the intramolecular metal-catalyzed 6-endo dig annulation of analagous alkynyl-oximes. Additionally, the discovery of a 5-exo dig annulation of related systems is discussed.

Despite progress in the metal-catalyzed synthesis of aromatic heterocycles, annulation routes towards 6-membered heterocycles remain underdeveloped. Specifically, routes towards pyridines are rare in spite of the prevalence of this moiety in novel drug candidates. Our initial efforts towards pyridines featured oximes as competent nucleophiles in the intramolecular, 6-exo dig annulation of alkynes using Brønsted acid catalysis. Two of the oxidation states required for subsequent aromatization are contained within the oxime via loss of water. An extension of this chemistry is presented and discussed, and involves the intramolecular metal-catalyzed 6-endo dig annulation of analagous alkynyl-oximes. Additionally, the discovery of a 5-exo dig annulation of related systems is discussed.