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Laboratoire d'innovation moléculaire et applications (Strasbourg / Mulhouse)

Overview
Works: 14 works in 14 publications in 2 languages and 14 library holdings
Roles: Other
Publication Timeline
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Most widely held works by Laboratoire d'innovation moléculaire et applications (Strasbourg / Mulhouse)
Original chiral scaffolds bearing P-stereogenic centres by Aabid Mohd( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

Organic compounds having chirality on phosphorous atom, are called P-stereogenic, P-chirogenic or P-chiral compounds. These compounds are widely used in agrochemistry, pharmacy, coordination chemistry and in organometallic asymmetric catalysis, as one of the most important classes of chiral ligands (Nobel Prize 2001; W. S. Knowles). However, access to these P-stereogenic compounds, is challenging due to the complex, tedious and multi-steps synthetic methodologies. Herein, we report a highly efficient novel methodology to access P-stereogenic compounds, which often involves dynamic kinetic resolution (DKR) under modified Atherton-Todd reaction conditions, using a racemic H-phosphinate and an enantiopure phenol bearing a chiral sulfoxide moiety. Furthermore, the newly obtained O-P coupling product can potentially be post-functionalised under mild conditions to obtain various original P-stereogenic scaffolds. Thus, these O-P coupling products can be considered as highly potential precursors to access a variety of original P-stereogenic molecules
Utilisation de la lumière visible pour la fonctionnalisation sélective de liaisons C-H d'hétérocycles azotés by Lucas Guillemard( )

1 edition published in 2019 in French and held by 1 WorldCat member library worldwide

The initial work presented in this manuscript revolves around a dual catalytic system merging photoredox catalysis and C-H bonds activation, two significant fields in modern organic chemistry. The objective was to combine these two distinct catalytic cycles in a synergistic way to perform unprecedented couplings while targeting eco-friendly chemistry. During our research studies, we discovered two new powerful methodologies allowing the C-H functionalization of N-heterocycles induced by visible-light irradiation. First, we developed a regiodivergent perfluoroalkylation of quinolines derivatives selectively at C5 and C8 positions. Furthermore, we designed a direct C-H acylation of N-heterocycles thanks to the visible-light irradiation of in situ generated Electron Donor Acceptor (EDA) complexes. Remarkably, these exceptionally mild and green radical transformations do not require any transition metal or photosensitizer and are compatible with a large panel of substrates. Subsequently, we had the ambition to control the axial chirality of N-heterobiaryls by adapting the previously disclosed protocols in an atroposelective fashion. In that respect, we used bifunctional organocatalysts able to establish hydrogen bonding interactions with the involved substrates in order to obtain a chiral induction
Etude de la réactivité des pyrimidines dans des réactions de Diels-Alder à demande électronique inverse by Vincent Le Fouler( )

1 edition published in 2019 in French and held by 1 WorldCat member library worldwide

La séquence ihDA/rDA est une transformation d'intérêt en synthèse organique en raison de la complexité structurelle à laquelle elle donne accès facilement. A ce jour l'utilisation des pyrimidines dans de telles séquences est encore peu explorée en raison de leur faible réactivité. Dans ce manuscrit sont décrites deux stratégies impliquant des pyrimidines dans une séquence ihDA/rDA pour la synthèse de 4-azaindolines et de 7-azaindazoles. Dans le cadre de la synthèse des 4-azaindolines, les travaux rapportés se concentrent sur la synthèse d'une série d'intermédiaires clés de la synthèse des 4-azaindolines, les N-vinylynamides. Dans le cadre des 7-azaindazoles, une synthèse en 3 à 5 étapes de l'hétérocycle est rapportée utilisant la séquence ihDA/rDA comme étape clé. 30 exemples sont illustrés, ainsi que les résultats faisant suite à un suivi de réactivité, une étude théorique, une montée en échelle et enfin une application concrète de cette nouvelle méthodologie par application sur un composé bioactif connu
Nouvelle stratégie d'accès aux diarylheptanoïdes cycliques : vers la synthèse totale du myricanol by Paul Masse( )

1 edition published in 2020 in French and held by 1 WorldCat member library worldwide

Macrocyclic diarylheptanoids are intriguing and promising due to both their architectural features and biological properties. In this context, the objective of this thesis is to develop a new approach to prepare this appealing family of compounds. In the one hand, we envisioned synthetizing myricanol, a strained 13-membered meta,meta-diarylheptanoid, through a Suzuki-Miyaura coupling and a ring-closing metathesis. This pathway led to the unintended formation of 26-membered head-to-tail dimers as a result of the actual ring strain. In the other hand, we describe herein the first, direct, rapid and versatile route to access the ortho,meta-diarylheptanoids family via a ring-closing metathesis strategy. Hence, we applied this method to the synthesis of actinidione, a natural product bearing a benzoquinone motif, in 14 steps with an overall yield of 18% and a high degree of ideality in the choice of the synthesis strategy
Vers de nouvelles méthodes d'introduction de groupements fluorés émergents : synthèse et réactivité d'azirines trifluorométhylthiolées by Thomas Guérin( )

1 edition published in 2019 in French and held by 1 WorldCat member library worldwide

In a context of the race to the discovery of novel reagents for the late-stage introduction of emergent fluorinated substituents (EFS), we worked on the development of new methodologies and new reagents to access various EFS-bearing structures. A first approach involving fluorinated carbon-centered radicals and arynes proved unsuccessful. In a second part we tried to synthetize a bismuth-centered trifluoromethoxylated complex. The inherent problems of this type of chemistry prevented us to isolate the targeted complexes. We managed however to propose an efficient methodology for the direct trifluoromethoxylation of alkyl iodides. We produced silver (I) trifluoromethanolate from ex situ-generated difluorophosgene. Finally, in an approach more oriented towards the early-stage introduction of the EFS we could synthetize several trifluoromethylthiolated azirines that reacted in situ with a variety of nucleophiles and ambiphiles
Etudes de complexes organométalliques formés par des calixarènes fonctionnalisés par des carbènes N-hétérocycliques by Rahma Aroua( )

1 edition published in 2018 in French and held by 1 WorldCat member library worldwide

A series of new calix[4]arenes bearing one or two imidazoliums units in the lower rim were synthesized as precursors of N-heterocyclic carbenes for the synthesis of the corresponding nickel complexes. All products obtained were characterized by NMR spectroscopy, microanalysis and mass spectroscopy and was revealed to be in cone conformation. The application of Ni-NHC-calix[4]arene in Suzuki-Miyaura cross coupling showed moderate to good conversions. This is been depending on the length of the alkyl chain and the number of the catalytic centers grafted on the platform
Biphényles à chiralité axiale : vers la synthèse de paires de Lewis frustrées pour la catalyse énantiosélective by Julien Bortoluzzi( )

1 edition published in 2018 in French and held by 1 WorldCat member library worldwide

After having developed a new method of deracemization of iodinated biphenyls allowing us, for the first time, to influence the diastereoselectivity of the trapping by the Andersen reagent, we have turned our attention to the use of this molecular scaffold in the design of new frustrated Lewis pairs bearing either a Lewis acidic group, a Lewis basic group or simultaneously both groups. We first accessed a new series of enantiopure biphenylphosphines that can find applications as Lewis base (including the field of frustrated Lewis pairs), as nucleophilic organocatalyst or as ligand in organometallic catalysis. Then, various methods were (re)developed to access chiral biphenyl-based Lewis acids: firstly, the functionalization of biphenyltrifluoroborate salts as chiral and enantiopure borane precursors and secondly the use of electrophilic silanes. The whole information and methodologies developed herein may be applied to the synthesis of new ambiphilic compounds as new atropo-frustrated Lewis pairs
Synthèses de biaryles atropoenrichis et de biphénylènes via des arynes substitués by David Augros( )

1 edition published in 2018 in French and held by 1 WorldCat member library worldwide

This work consisted in the study of the “aryne coupling”, a transition-metal free process to access biaryl moieties, which involves the reaction between two in situ generated intermediates: a nucleophilic aryllithium derivative and an electrophilic aryne. This work resided in the optimization of the atropoenantioselective version of the aryne coupling and its application to the formal synthesis of (-)-steganacin. We then moved to the atropoenantioselective version of the reaction, by introducing chiral ligands in the reaction mixture, which aim was to coordinate the aryllithium species and to transfer their chiral information to the biaryl axis. After optimization of various reaction parameters, some enantiomeric excesses were obtained as well as various side products in some cases, among which biphenylene derivatives. According to the potential applications of these compounds, another part of this work was dedicated to their synthesis by means of aryne dimerization reactions
Study of the mechanism of action of metallic active oxygen barriers applied in polymers for food and drinks preservation by Angéline Cherbonnel( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

Plastics are becoming the most used material for food and drinks preservation. Despite their numerous advantages (transparency, price, modularity, gas barrier property), their oxygen barrier properties have to be improved to avoid hazardous oxidation reactions to foods and drinks and so to increase their shelf-life. One alternative to solve this problem is to combine polymers and metal catalysts to scavenge oxygen. This possible strategy was investigated during this Ph.D. project. After a first introductive chapter, the second depicts the physico-chemical properties of selected metal catalysts (stability, protonation constants, complexation constants towards cobalt(II) and manganese(II), oxygenation capacity, electrochemistry). The third chapter is devoted to their use as powerful oxidant of organic substrate. Finally, the last chapter is dedicated to a solid-state study of polymer oxidation in the presence of metal catalysts. A large part of this last chapter has been devoted to the thorough elucidation of the nature/structure of the oxidized product(s)
Structure of cationic CNHC,Calkyl nickelacycles and their activity in the catalytic functionalization of the C-H bonds of azoles by Bernardo Rosa Lourenço de Pina Cardoso( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

Cette thèse développe l'étude des complexes de nickel(II) porteurs de ligands carbènes N hétérocycliques (NHC) selon deux axes: la synthèse et la caractérisation de complexes nickelacycliques avec un ligand chélatant carbone-carbone (CNHC, Calkyl); et leur activité catalytique dans la construction des liaisons carbone-carbone (Csp2-Csp2/Csp3) des 1-chalcogènes-azoles par fonctionnalisation des liaisons carbone-hydrogène (C-H). Une série de produits d'addition d'acétonitrile métallacycliques CNHC,Calkyl-Ni(II) cationiques a été synthétisée par élimination d'un ligand cyclopentadiényle des nickelacycles demi-sandwich a 18 électrons de valence parents. Il a été déterminé que les complexes cationiques existaient en tant qu'espèce Ni(II) à 14 électrons de valence en forme de T, insaturée de manière coordonnée et électronique, à l'état solide. L'application de ces nouveaux complexes au couplage croisé du benzothiazole avec les iodoarènes s'est avérée une stratégie efficace dans la formation des liaisons Csp2-Csp2, par la combinaison d'un échafaudage métallacyclique stabilisant avec des ligands labiles. La découverte d'une espèce demi sandwich Ni(II)-(NHC)-(benzothiazolyle) inactif dans l'arylation du benzothiazole, mais actif dans le couplage du benzothiazole avec les iodoalcanes, constitue le premier exemple de construction des liaisons Csp2-Csp3 du benzothiazole avec un catalyseur Ni(II)-NHC
Sulfoxydes : novel strategy for the asymmetric C(sp3)-H activation by Soufyan Jerhaoui( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

Pendant de nombreuses années, les liaisons C-H aliphatiques ont été considérées comme dormantes, difficilement exploitables dans le contexte de la chimie organique. Le défi le plus important est de sélectionner une liaison C-H parmi toutes celles que contient une molécule. L'approche la plus utilisée à ce jour est l'utilisation d'un groupement directeur qui permet, en se liant à un métal, de diriger l'activation d'une liaison C-H en particulier. Suite au développement des groupements bicoordinants, nous avons développé notre propre groupement bicoordinant chiral. Cet auxiliaire nous a permis de réaliser de nombreuses transformations diastéréosélectives sur des carbones aliphatiques telles que l'arylation et l'oléfination. Nous l'avons également utilisé pour développer une méthodologie innovante pour la synthèse de produits naturels. Suite à ces travaux, nous avons développé un nouveau ligand chiral qui a été utilisé dans l'arylation et l'alkynylation énantiosélectives de cycloalcanes
Nouvelles voies de synthèse énantiosélective pour l'accès à des composés difluorométhylés by Chloé Batisse( )

1 edition published in 2018 in French and held by 1 WorldCat member library worldwide

 
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Alternative Names
LIMA

UMR 7042

Languages
French (10)

English (4)