Reductive functionalization of CO2 with amines: an entry to formamide, formamidine and methylamine derivatives

International audienceCO2 utilization for the production of C1-containing molecules is a desirable route to value-added chemicals. In this perspective, we summarize the recent results devoted to the formation of nitrogen compounds obtained by reductive functionalization of CO2 in the presence of amines. Using mild reductants, such as molecular hydrogen, hydrosilanes and hydroboranes, novel catalytic reactions have been designed in the last few years to facilitate the reductive functionalization of CO2 to formamide, formamidine and methylamine derivatives. While early efforts were devoted to the formylation of N-H bonds, efficient organic and metal catalysts have been developed lately to promote the complete deoxygenation of CO2 to benzimidazoles, quinazolinones, formamidines and methylamines. Finally, the opportunities and challenges facing the practical use of CO2 in the production of nitrogen-containing molecules are discussed

Synergistic effects in ambiphilic phosphino-borane catalysts for the hydroboration of CO2_2

International audienceThe benefit of combining both a Lewis acid and a Lewis base in a catalytic system has been established for the hydroboration ofCO$_2$, using ferrocene-based phosphine, borane and phosphino-borane derivative

Nasal oral fistula revealing Langerhans´ cell histiocytosis in adult patient: case report

Langerhans cell histiocytosis (LCH) is a rare systemic disease caused by proliferation of mature histiocytes; its association to histiocyto fibroma is rarely reported. It rarely affects adults. We report a case of systemic LCH, in an adult patient with osteolytic lesion causing a fistula between the left nasal cavity and hard palate, involving the bone, lung, lymph node and associated to multiple histiocyto fibroma. The patient was operating for a fistula, and he was treated by chemotherapy and corticosteroids. Langerhans´ cell histiocytosis is a rare case, especially in adult patient. The diagnosis was based on histological and immunohistochemical analyses. This patient was treated by steroids and chemotherapy

Copper catalysed arylation of nucleophiles

Au cours de cette thèse, plusieurs nouvelles méthodes d'arylation de nucléophile (oxygéné, azoté et carboné) ont été mises au point ainsi qu'une étude mécanistique. Dans le cadre du projet ANR, nous avons réalisé des travaux dans ce domaine dans le laboratoire du Dr Anny Jutand à L'ENS Paris. D'un point de vue général, nous pouvons donc dire que nos méthodes se situent bien en phase avec les critères de la réglementation européenne visant à diminuer l'impact des produits chimiques sur l'environnement (REACH) par la recherche de nouvelles voies de synthèse moins toxiques et moins polluantes. Travaux en cours et perspectives : Par rapport aux réactions faisant intervenir des catalyseurs au palladium, celles impliquant le cuivre ont très peu été étudiées du point de vue de leur mécanisme. Les premiers travaux concernant le mécanisme de l'arylation de nucléophiles catalysé au cuivre ont débuté depuis seulement quelques années et ont conduit à environ une dizaine de publications. Malgré quelques avancées significatives, beaucoup reste à faire.In this thesis, several new methods of nucleophilic arylation (oxygen, nitrogen and carbon) were developed and a mechanistic study. As part of the ANR project, we have carried out work in this field in the laboratory of Dr. Anny Jutand at ENS Paris. From a general point of view we can say that our methods are well in line with the requirements of European regulations to reduce the impact of environmental chemicals (REACH) by the search for new synthetic routes less toxic and less polluting. Work in Progress and prospects : Compared to reactions involving palladium catalysts, those involving copper have been studied very little in terms of their mechanism. Early work on the mechanism of arylation of nucleophiles catalyzed copper began last few years and led to about a dozen publications. Despite some significant advances, much remains to be done

Copper catalysed arylation of nucleophiles

Au cours de cette thèse, plusieurs nouvelles méthodes d'arylation de nucléophile (oxygéné, azoté et carboné) ont été mises au point ainsi qu'une étude mécanistique. Dans le cadre du projet ANR, nous avons réalisé des travaux dans ce domaine dans le laboratoire du Dr Anny Jutand à L'ENS Paris. D'un point de vue général, nous pouvons donc dire que nos méthodes se situent bien en phase avec les critères de la réglementation européenne visant à diminuer l'impact des produits chimiques sur l'environnement (REACH) par la recherche de nouvelles voies de synthèse moins toxiques et moins polluantes. Travaux en cours et perspectives : Par rapport aux réactions faisant intervenir des catalyseurs au palladium, celles impliquant le cuivre ont très peu été étudiées du point de vue de leur mécanisme. Les premiers travaux concernant le mécanisme de l'arylation de nucléophiles catalysé au cuivre ont débuté depuis seulement quelques années et ont conduit à environ une dizaine de publications. Malgré quelques avancées significatives, beaucoup reste à faire.In this thesis, several new methods of nucleophilic arylation (oxygen, nitrogen and carbon) were developed and a mechanistic study. As part of the ANR project, we have carried out work in this field in the laboratory of Dr. Anny Jutand at ENS Paris. From a general point of view we can say that our methods are well in line with the requirements of European regulations to reduce the impact of environmental chemicals (REACH) by the search for new synthetic routes less toxic and less polluting. Work in Progress and prospects : Compared to reactions involving palladium catalysts, those involving copper have been studied very little in terms of their mechanism. Early work on the mechanism of arylation of nucleophiles catalyzed copper began last few years and led to about a dozen publications. Despite some significant advances, much remains to be done

From Academia to the Market – Air-stable Ni(II)/Josiphos Catalysts

The design, synthesis, commercialization and application of air stable Ni(II)/Josiphos complexes has been realized in a collaboration between Solvias and ICBMS (University Lyon 1). The Ni-complexes  are utilized as versatile precatalysts for diverse cross coupling reactions. Apart from being active in established C–C and C–N couplings at low catalyst loadings, the novel Ni-precatalysts enabled the development of the challenging monoarylation of ammonia, ammonia surrogates and even alkylammonium chlorides with aryl carbamates. Finally, the alpha-arylation of acetone with aryl chlorides, carbamates and pivalates was demonstrated using the Ni(II)/Josiphos precatalysts

Acridinium Salts and Cyanoarenes as Powerful Photocatalysts: Opportunities in Organic Synthesis

International audienceThe use of organic photocatalysts has revolutionized the field of photoredox catalysis as it allowed access to new reactivities that were traditionally restricted to transition metal photocatalysts. In this review we focus our attention onto two classes of organophotocatalysts, namely acridinium ions and cyanoarenes derivatives that have demonstrated remarkable activities in large variety of organic transformations. Specifically, the use of those photocatalysts in oxidative quenching processes will be discussed with a special focus on their mechanistic aspects

Transition-Metal-Catalyzed Monoarylation of Ammonia

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Ullmann Condensation Today: Arylation of Alcohols and Thiols with Aryl Halides

International audienceThis chapter surveys C(aryl)--O and C(aryl)--S bond-forming reactions via copper-catalyzed couplings of oxygen (water, alcohols, phenols) and sulfur (thiols, thiophenols) nucleophiles with aryl halides. Among the increasing number of publications related to this topic, the chapter focuses mainly on the most significant results and important breakthroughs that have been reported in the last 10 years or so. Its scope highlights the most efficient homogeneous and heterogeneous catalytic systems based on the association of a copper source with or without an original ligand. The reaction of aliphatic alcohols with aryl halides mediated by copper (Ullmann condensation) is clearly a classical transformation that has been known for a long time for the synthesis of alkyl aryl ethers. The diaryl ether linkage constitutes an important structural motif that can be found in a variety of agrochemicals, as well as in important molecules from the pharmaceutical industry and polymer sciences

Direct Synthesis of Carbamoyl Fluorides by CO 2 Deoxyfluorination

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