L'utilisation du cobalt en synthèse et catalyse organiques est reconnue depuis les années 1970, notamment dans la réaction de Pauson-Khand. Dès lors, de nombreux systèmes catalytiques au cobalt ont prouvé leur efficacité dans diverses transformations chimiques telles que les cycloadditions [2+2+2] ou l'activation des liaisons C(sp2)-H. Dans ce manuscrit, sont présentés des transformations chimiques basées sur l’utilisation de catalyseurs au cobalt s’effectuant essentiellement avec économie d’atomes, et les essais de développement des versions énantioselectives.Tout d'abord, l'activité de catalyseurs au cobalt(I) a été établie dans la réaction de cycloisomérisation de diènynes pour obtention de bicycles[4.3.0]. Les études concernant différents paramètres du système catalytique ainsi que le champ d'application sont présentés. Les catalyseurs à base d'acétate de cobalt(II) se sont révélés très efficaces pour les réactions d'hydroalcynylation. L'hydroalcynylation de vinylaziridines a été développée après optimisation du système catalytique et, le domaine d’application selon la nature des réactants a été défini. Finalement, les études préliminaires de l'allylation énantiosélective avec les catalyseurs de cobalt(II) ont été réalisées. Ceux-ci se sont révélés plutôt comme activateurs du groupement carbonyle, compromettant la version asymétrique de la réaction / The application of cobalt in organic synthesis and catalysis has been known since the 1970s, especially in Pauson-Khand reaction. Until now, a lot of catalytic systems with cobalt have demonstrated their efficiency in various chemical transformations including [2+2+2] cycloadditions or the activation of C(sp2)-H bonds. In this manuscript are presented the chemical transformations based on the use of cobalt to catalyze atom-economical reactions, and the attempts to develop enantioselective versions. First of all, the activity of cobalt(I) catalysts was established for the cycloisomerisation reaction of dienynes giving bicycles[4.3.0]. The studies of different parameters of the catalytic system, as well as the scope reaction, will be presented. Moreover, the catalysts based on cobalt(II) acetate proved to be very efficient for hydroalkynylation reactions. The hydroalkynylation reaction of vinylaziridines was developed after catalyst optimisation and, the scope reaction according to the nature of reactants was defined. Finally, preliminary studies of enantioselective allylation using cobalt(II) catalysts were performed. These promoters were found to be activators of the carbonyl group, thus compromising the asymmetric version of the reaction

Thesis advisor: Shih-Yuan Liu / Thesis advisor: Amir H. Hoveyda / Chapter 1. Senphos–Palladium-Catalyzed cis-Carboboration of Internal 1,3-Enynes with Carbon–Bound Boron Enolates: Reaction Development and Mechanistic Analysis. A new family of carbon-bound boron enolates (C–boron enolates) that are created through a kinetically controlled halogen exchange process between B–chlorocatecholborane and silylketene acetals is presented. These C–boron enolates are demonstrated to activate 1,3-enynes substrates in the presence of a Senphos-Pd complex to achieve carboboration reaction of an alkyne unit. This carboboration reaction produced highly substituted dienyl boron building blocks in high site-, regio-, and diastereoselectivity. A combined experimental and computational study of this carboboration reaction by Density-Functional Theory (DFT) calculations, 31P NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis will also be described. Mechanistic study supports a syn outer-sphere oxidative addition mechanism featuring a Pd-π-allyl intermediate followed by coordination-assisted rearrangement instead of the conventional inner-sphere β-migratory insertion mechanism. Chapter 2. trans-Hydroalkynylation of Internal 1,3-Enynes Enabled by Cooperative Catalysis. A trans-hydroalkynylation reaction of internal 1,3-enynes enabled by a cooperative catalysis system that comprises of Senphos–Pd complex, tris(pentafluorophenyl)borane, copper(I) bromide, and 2,2,6,6-tetramethylpiperidine, is described. The tris(pentafluorophenyl)borane as Lewis acid catalyst is shown to promote the reaction involving the emerging outer-sphere oxidative reaction step. This hydroalkynylation reaction affords the cross-conjugated dieneynes that serve as versatile synthons for organic synthesis. The photophysical properties of these cross-conjugated dieneynes depend on the position of electron donor/acceptor substituents along the conjugation path, as characterized by UV–vis absorption and emissions spectroscopy. Chapter 3. Senphos–Palladium/B(C6F5)3-Catalyzed trans-Hydrothiolation of 1,3-Enynes: Reaction Development and Mechanistic Analysis. A trans-hydrothiolation reaction of 1,3-enynes enabled by a cooperative catalysis system that comprises of Senphos–Pd complex and tris(pentafluorophenyl)borane is detailed. The tris(pentafluorophenyl)borane is shown to alter the reaction pathway, leading to a trans-addition product over cis-addition one. Experimental mechanistic study that includes 31P NMR, kinetic study, kinetic isotope effect (KIE) study, Hammett analysis, is consistent with a cooperative activation mechanism that features an outer-sphere protonation step. / Thesis (PhD) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.