The intramolecular Friedel-Crafts acylation of aromatics with Meldrum?s acid derivatives catalyzed by metal trifluoromethanesulfonates and other Lewis acids is reported. Meldrum?s acids are easily prepared, functionalized, handled, and purified. The synthesis of polysubstituted 1-indanones from benzyl Meldrum's acids was investigated thoroughly, and it was shown that a variety of catalysts were effective, whilst accommodating a diversity of functional groups under mild conditions. The scope, limitations, and functional group tolerance (terminal alkene and alkyne, ketal, dialkyl ether, dialkyl thioether, aryl methyl ether, aryl TIPS and TBDPS ethers, nitrile- and nitro-substituted aryls, alkyl and aryl halides) for a variety of 5-benzyl (enolizable Meldrum?s acids) and 5-benzyl-5-substituted Meldrum?s acids (quaternarized Meldrum?s acids), forming 1-indanones and 2-substituted-1-indanones respectively, are delineated. <br ><br /> This method was further applied to the synthesis of 1-tetralones, 1-benzosuberones, and the potent acetylcholinesterase inhibitor donepezil. <br ><br /> Mechanistic investigations were undertaken to determine the rate-determining step in the acylation sequence using Meldrum?s acid, as well as to examine the role of the Lewis acid catalyst. Enolizable Meldrum?s acid derivatives can react via an acyl ketene intermediate under thermal conditions, while quaternarized Meldrum?s acid derivatives are thermally stable and only act as effective Friedel-Crafts acylating agents in the presence of a Lewis acid catalyst. <br ><br /> The total synthesis of (±)-Taiwaniaquinol B was completed. This natural product was the first ever isolated containing an unusual 6-5-6 fused ring system, and it also contains a hexasubstituted aromatic ring, and two all-carbon quaternary centers. This synthesis was accomplished via an intramolecular Friedel-Crafts acylation/carbonyl a-<em>tert</em>-alkylation reaction that exploits the unique chemistry of Meldrum?s acid. This novel methodology can be used to access a variety of highly substituted fused ring systems of various sizes.

A new method for the efficient synthesis of ferrocenylenones was developed. Acryloyl, methacryloyl, crotonyl, cinnamoyl, and &amp / #946 / -methylcrotonyl chlorides reacted with ferrocene in the presence of a Lewis acid (EtAlCl2 or EtAlCl2-Me3Al) to give the corrosponding ferrocenylenones (acryloyl, methacryloyl, crotonyl, cinnamoyl, and &amp / #946 / -methylcrotonylferrocenes) in good isolated yields. Using the Gabriel-Cromwell reaction, acryloyl and crotonoylferrocenes were converted to the novel ferrocenyl substituted aziridines with benzylamine, isopropylamine and furfurylamine. The aziridines were isolated in good to excellent yields.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1955. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 171-180).

Zugl.: Karlsruhe, Univ., Diss., 2009

Made available in DSpace on 2016-06-02T20:15:18Z (GMT). No. of bitstreams: 1 1960.pdf: 10381131 bytes, checksum: 5638ec0c0a5f463febc74da13a4f7c30 (MD5) Previous issue date: 2006-08-02 / Financiadora de Estudos e Projetos / The fundamental magnetic properties of chromium and its alloys Cr(1¡x)Nb(x) and Cr(1¡x)V(x), were investigated with the aim to achieve a better comprehension about the nature of the spin density waves. Was dened the edge between the AF1 and AF2 phases on the Cr(1¡x)Nb(x) alloys as function of niobium concentration. Using x-rays di®raction techniques was studied de formation of antiferromagnetic domains in the surfaces with [001] direction of chromium samples. As observed, cooling the sample under applied magneticeld do not create new magnetic domains, actuating only on its reorien- tation. The magnetic history of sample does not in°uence the surface magnetic domains formation, been an exclusive property of the sample surface crystalographic orientation. Was observed the formation of localized magnetic moment on paramagnetic phase of Cr(1¡x)Nb(x) alloys. This phenomenon early studied in Cr(1¡x)V(x) alloys, shown important qualitative di®erences which are explained on Friedel oscillations picture generated by impurity atoms. Was realized x-rays di®raction experiments which provided evidences of the existence of Friedel oscillations in Cr(1¡x)V(x) alloys. / As propriedades magnéticas fundamentais do cromo e de suas ligas de Cr(1¡x)Nb(x) e Cr(1¡x)V(x), foram investigadas com o objetivo de melhorar a compreensão sobre a natureza das ondas de densidade de spin (spin-density-wave). Foi determinada a fronteira entre as fases AF1 e AF2 nas ligas Cr(1¡x)Nb(x) em função da concentração de nióbio. Utilizando tecnica de difração de raios-x foi estudada a formação dos dominios antiferro-magnéticos nas superfícies paralelas às direções [001] e [111] de uma amostra de cromo crescida por transporte qumico de vapor (chemical vapor deposition method). Os resultados obtidos com o estado de monodomínio volumétrico preparado por resfriamento das amostras com campo magnético aplicado, comparados com aqueles das amostras em estado multi-domínio volumétrico e monodomínio de superfície, levam a conclusão de que a aplicação de campo magnético ou de outra maneira, a história magnética da amostra, não implica na formação de novos domínios magnéticos na superfície do cromo e que o campo magnético atua especificamente na reorientação do domínios existentes. Portanto, a formação de monodomínios superficiais e uma propriedade exclusiva da orientação cristalografica da superfície da amostra. Foi observada a formação de momento magnético localizado na fase paramagnética das ligas de Cr(1¡x)Nb(x). Esse fenômeno, anteriormente estudado nas ligas Cr(1¡x)V(x), apresentou diferenças qualitativas importantes na sua manifestação nas ligas de Cr(1¡x)Nb(x), que são explicadas a partir das oscilações de Friedel que se formam na região dos átomo de vanadio e nióbio. Foram realizados experimentos de difração de raios-x que forneceram evidências da existência das oscilações de Friedel nas ligas Cr(1¡x)V(x).

Le développement d'une nouvelle voie de synthèse de poly(éther cétone cétone),polymères thermostables, a été étudiée pour des matériaux composites à matrice thermoplastique obtenus par le procédé de moulage par injection de résine RTM. Pour cela,nous nous sommes orientés vers une polymérisation par couplage réactif entre des monomères difonctionnels et des agents de couplage. Neuf monomères X-EKKE-X avec différentes extrémités réactives ont été synthétisés par acylation de Friedel-Crafts ou substitution nucléophile aromatique puis caractérisés structurellement et thermiquement.Des essais de couplage à partir de monomères à extrémités COOH sur des bisoxazoline sont permis la synthèse en masse de quatre polymères, semi-cristallins ou amorphes, de faibles masses molaires. A travers l'étude du comportement thermique de molécules modèles, une fragilité thermique à partir de 250°C a été mise en évidence pour ces polymères et attribuée au pont ester-amide entre deux unités EKKE. / A new synthetic route to poly(ether ketone ketone), thermostable and semi-crystalline polymers, has been studied towards composite materials with a thermoplastic matrix obtained by a resin transfer molding process (RTM). This original synthesis was conducted by coupling reactions between difunctionals monomers and coupling agents. Nine X-EKKE-X monomers with different reactive extremities have been synthesized by Friedel-Crafts acylation or nucleophilic aromatic substitution. Thermal and structural properties were thoroughly investigated. Four polymers with semi-crystalline or amorphous morphologies and low molecular weights were obtained by coupling reactions between monomers with COOH functional extremities and bisoxazolines. Through the study of the thermal behavior of models molecules, a thermal fragility was highlighted for these polymers from 250°C and assigned to the amide-ester bridge between two EKKE units.

Les réactions permettant la création de liaisons carbone-carbone sont des outils essentiels dans le domaine de la synthèse organique. Elles permettent d'accéder à des structures de plus en plus complexes. Cependant le contrôle de ces réactions en utilisant des partenaires hautement fonctionnalisés reste un enjeu majeur.Le développement de nouvelles méthodologies de synthèse basées sur la réactivité des acrylamides chiraux dérivés d'acides aminés est étudié dans ces travaux. Une nouvelle version de la réaction d'alkylation de pyrroles de type Friedel-Crafts a été développée en utilisant le caractère électrophile d'acrylamides chiraux hautement fonctionnalisés. Le pyrrole peut être monoalkylé ou dialkylé de façon sélective conduisant à de nouvelles structures hétérocycliques portant des enchaînements peptidiques pouvant contenir jusqu'à quatre résidus d'acides aminés. Les acrylamides chiraux portant un motif allyltriméthylsilane conjugué ont été utilisés comme nouveaux réactifs permettant des réactions d'allylation hautement diastéréosélectives et chimiospécifiques vis-à-vis d'aldéhydes. L'extension de cette méthodologie aux aldéhydes α- aminés a été réalisée et permet un accès aisé à des structures analogues des acides γ-aminés. / Reactions allowing carbon-carbon bond creation are essential tools in the field of organic synthesis. These reactions are used to access to more and more complex structures. However their control in the case of highly functionnalized partners is still a serious concern.Development of new methodologies based on the reactivity of aminoacid derivating chiral acrylamides is reported. A new version of pyrrole alkylation reaction was developed using the electrophilic behaviour of highly functionnalized chiral acrylamides. Pyrrole can be selectivly monoalkylated or dialkylated leading to new heterocyclic structures bearing peptidic sequences containing up to four aminoacids residues. Chiral acrylamides bearing a conjuguated allyltrimethylsilane moiety have been used as new reagent in highly diastereoselective and chemospecific towards aldehydes allylation reactions. This methodology was extended to α-aminoaldehydes allowing easy access to γ-aminoacidsanalogues.

Syringolin A, a plant elicitor, was isolated in 1998 and has been identified as a potential anti-cancer compound based on its activity against proteasome. The unique structure of this natural product consists of a 12-membered diamide ring, formed by two non-proteinogenic amino acids 3,4-dehydrolysine and 5-methyl-4-amino-2-hexenoic acid, and a bis(valinyl)urea side chain which is connected to the macrocycle by a peptide bond. The construction of this challenging macrocylic core was achieved by a macrolactamization reaction using peptide coupling reagents BOP/HOAt, while the two (E)-configured double bonds in the ring were introduced by a Johnson-Claisen rearrangement and Wittig olefination respectively. Ru(bpy)3Cl2 which is an excellent visible light photoredox catalyst, has been extensively applied to organic syntheses in recent years. Although much research has focused on the study of the reductive quenching pathway, the oxidative quenching pathway has rarely been explored. Using persulfate as the electron acceptor, we have successfully developed a protocol for the oxidative functionalization of dialkylamides under mild reaction conditions. Further application has demonstrated a Friedel-Crafts amidoalkylation methodology applying various nucleophilic alcohols and arenes. The reaction can also be conducted under thermolysis condition without the photocatalyst, but requires elevated temperature. Both of the reactions generate N-acyliminium ion in situ as the key intermediate. The first example of photocatalytic halogenation has been achieved at room temperature using Ru(bpy)3Cl2 and polyhalomethanes (CBr4 and CHI3) as the electron acceptors. Excellent yields and high functional group tolerance have been established. Mechanistic studies indicate a single electron transfer (SET) pathway and the transformation is via a Vilsmeier-Haack type intermediate. Further expansion of this methodology to anhydride formation was achieved, providing a mild avenue for the synthesis of symmetric anhydrides. Furthermore, the use of a continuous flow reactor enabled the efficient large scale synthesis of anhydrides.

Philosophiae Doctor - PhD / The catalytic support materials used in the present study are zeolite HBEA and MCM-41. These high silica zeolites were synthesised from coal fly ash (CFA) waste via a novel approach that involved a fusion step, acid assisted silica extraction and removal of Al, Ca and Na from the silica by treatment with oxalic acid. The generated silica was converted to HBEA and MCM-41 via conventional hydrothermal treatment. The metal incorporation onto HBEA was done via two approaches namely; liquid phase ion exchange (LIE) and wet impregnation (WI) while the loading on MCM-41 was only done via WI since the material does not possess exchange sites. The metal solution precursors were AMD and Fe extracted from CFA (FeAsh) via acid leaching followed by pH regulation by concentrated NaOH. This is the first time these solutions were tested as possible metal precursors in catalyst synthesis. / 2021-08-30

Stereodivergent and enantiodivergent pathways for the Friedel–Crafts reactions were computationally studied with DFT methods. This study aims to explain recently observed solvent-dependent regioselectivity, and enantioselectivity when cinchona catalyst is used. Deprotonation reaction, Frontier Kohn-Sham orbitals, dual descriptors, Mulliken charges, and Hirshfeld atomic charge for reactant were calculated and analyzed. The most probable position of electrophilic attack and nucleophilic attack in-silico predicted aligns with experimental observations. The calculation of the transition states on the anionic and neutral model in a vacuum show preference for the electrophilic attack in the para position. In comparison to the anionic system, the presence of potassium cation improves ortho/para selectivity and increases the energy barrier. For the key enantioselective step, 12 transition states were calculated which covers 4 representative product such: (R)-ortho, (S)-ortho, (R)-para, and (S)-para. The computational study suggests, that the presence of the cesium cation is essential for the arrangement of the reactant and catalyst in the transition state, which leads to observed selectivity.