To form Cu interconnects, dual-damascene techniques like chemical mechanical planarization (CMP) and post-CMP became inevitable for removing the "overburden" Cu and for planarizing the wafer surface. During the CMP processing, Cu interconnects and barrier metal layers experience different electrochemical interactions depending on the slurry composition, pH, and ohmic contact with adjacent metal layers that would set corrosion process. Ruthenium as a replacement of existing diffusion barrier layer will require extensive investigation to eliminate or control the corrosion process during CMP and post CMP. Bimetallic corrosion process was investigated in the ammonium citrate (a complexing agent of Cu in CMP solutions) using micro test patterns and potentiodynamic measurements. The enhanced bimetallic corrosion of copper observed is due to noble behavior of the ruthenium metal. Cu formed Cu(II)-amine and Cu(II)-citrate complexes in alkaline and acidic solutions and a corrosion mechanism has been proposed. The currently used metallization process (PVD, CVD and ALD) require ultra-high vacuum and are expensive. A novel method of Si surface metallization process is discussed that can be achieved at room temperature and does not require ultra-high vacuum. Ruthenation of Si surface through strong Si-Ru covalent bond formation is demonstrated using different ruthenium carbonyl compounds. RBS analysis accounted for monolayer to sub-monolayer coverage of Si surface. Interaction of other metal carbonyl (like Fe, Re, and Rh) is also discussed. The silicon (111) surface modifications with vinyl terminated organic compounds were investigated to form self-assembled monolayers (SAMs) and there after these surfaces were further functionalized. Acrylonitrile and vinylbenzophenone were employed for these studies. Ketone group of vinylbenzophenone anchored to Si surface demonstrated reactivity with reducing and oxidizing agents.

Dizertační práce pojednává o studiu, syntéze a chemické derivatizaci molekul spadajících do skupiny organických vysoce výkonných pigmentů a jejich potenciálním uplatnění v oblastech organické elektroniky. Teoretická část práce je zaměřena na nejnovější trendy v dané oblasti, a to jak z aplikačního potenciálu konkrétních derivátů, tak z pohledu syntetických možností a jejich strukturálních derivatizací. V experimentální části je pak podrobně popsána příprava pestré škály intermediátů a výsledných produktů, zahrnujících deriváty diketopyrrolopyrrolů (DPP), benzodifuranonu (BDF), epindolidionu (EP), naphthyridinedionu (NTD) a polymeru na bázi thiofenu (PT). Celkově bylo nasyntetizováno 103 molekul, přičemž 49 tvořily výsledné produkty, z nichž 27 bylo zcela nových, dosud nepublikovaných. Hlavním motivem derivatizace molekul pigmentů je zde inkorporace derivátů adamantanu do finálních struktur. V další části práce jsou blíže diskutovány jednotlivé chemické modifikace vedoucí k výsledným produktům. Na sérii N,N'-; N,O'- a O,O'-substituovaných derivátů DPP je popsána komplexní studie vlivu charakteru alkylových řetězců a také pozice jejich navázání v molekule DPP, a to nejen na selektivitu reakce, ale rovněž na optické i termické vlastnosti syntetizovaných produktů.

By flavin's unique structure, nature predestined riboflavin and its derivatives to the participation in redox processes within the bodies of all the living organisms. These biomolecules draw attention with intriguing optical properties and photosensitising abilities. Nature-inspired flavin derivatives share these qualities, and there is also a possibility of fine-tuning for the particular application from the chemical point of view. The thesis deals with two main aims. The first aim handles the synthesis of the trimer heteroaromatic precursor and 1,2-diketone. These key intermediates are essential for the future synthesis of the central aromatic core of the novel NH-free non-fused flavin derivative. The thesis introduces and verifies three approaches, including oxidation of diarylalkynes, nucleophilic addition of a corresponding organolithium compound to a Weinreb amide and benzoin condensation. The second aim covers the properties customization of NH-free fused systems by implementation of linear and bulky alkyl side-chains on the nitrogen atoms N1 and N3 of the alloxazine dilactam. N,N-alkylation introduced an increase in solubility in common organic solvents dichloromethane and chloroform. For the derivatives with 2-(adamantan-1-yl)ethyl substituents, high thermal stability was observed via TGA.

This study analyzes the reactivity and selectivity of Friedel-Crafts alkylations using benzylic alcohols and phenols in the presence of a Lewis acid, to synthesize methoxylated bisphenols as a benign alternative to BPA. The degree of methoxylation on the electrophile appears to affect the yield of the reaction while the degree of methoxylation on the nucleophile appears to affect the selectivity. A more methoxylated electrophile results in a lower yield whereas a more methoxylated nucleophile results in a change in ratio between the bisphenol isomers and/or causes other isomers to form. Neither the yield nor the selectivity appears to be affected significantly by the temperature.

No description available.

No description available.

Carbene ligands over these years have become a heavily utilizes and effective ligand for catalysis. The diamino carbene class of ligands are slightly less understood. The effects of bis(carbene) ligand structures of palladium (II) catalysts were investigated using the ETS-NOCV method. The results showed that the amount of π-backbonding played a major role in the rate of the reaction for these NHC complexes. The amount of pi acceptance from the ligand increased in correlation to the length of the methylene linkage in the ligand back bone resulting in increased catalytic activity. The ETS-NOCV method was used to determine the deformation densities that had a contribution to this interaction based on visual interpretation. The percent contribution of pi interactions provided a linear correlation to the natural log of the initial reaction rate, indicating that π-backbonding plays a crucial role in the overall catalytic activity of the palladium complexes. Gold (I) bis acyclic diamino carbenes (ADCs) were investigated for the possibility to be strong hydrogen bond catalysts. The ligand motif of the gold (I) bisADCs were found to be analogous thiourea compounds. Based on NBO analysis there were some improvements to hydrogen bond donicity in comparison to thioureas with the same functional group. The complexes were analyzed for hydrogen bond interactions and polarizations interactions between simple nitroolefin substrate and the catalyst using ETS-NOCV. Results showed that the compounds can form a stable hydrogen bonding system and activate the substrate. This capability is tunable by changing the electron withdrawing properties of the ligase motif, providing the idea that gold (I) bisADCs have potential to be good hydrogen bond catalysts. New thiourea-like gold (I) catalysts utilizing the acyclic diamino carbene motif that were hypothesized were synthesized using a one pot synthesis approach utilizing a metal templated synthesis method. The synthesis, characterization, and application prove these complexes with their cationic centers and bisADCs ligand motif can be utilized for Friedel-Crafts alkylation of indoles, resulting in the production of three new compounds to literature. This research also provided a new application for this specific ligand class and further proved the robustness of ADC ligands.

Yes / CC-1065, the duocarmycins and yatakemycin are members of a family of ultrapotent antitumour antibiotics that have been the subject of extensive investigations due to their mode of action and potential in the design of new anticancer therapeutics. The natural products and their analogues exert their effects through a sequence selective alkylation of duplex DNA in the minor groove at the N3 of adenine. An understanding of their structure and its effect on biological activity has been derived through chemical synthesis and has also generated new potential lead compounds. These studies form the first section of the review. The desire to progress these compounds to clinic has also led to studies of bioconjugation and prodrug formation and this is discussed in the second section of the review. The combination of synthesis with key biological experiments is a powerful tool to define the requirements for the development of natural products as potential therapeutic agents. The studies described herein form an excellent paradigm for the study and development of other natural products. / EPSRC, Yorkshire Cancer Research, Big C Cancer Research, UCB Pharma

Les alcaloïdes Daphniphyllum constituent une vaste famille de produits naturels isolés à partir de plantes à feuillage persistant couramment utilisés dans la médecine chinoise traditionnelle. Ils affichent une gamme impressionnante d'activités biologiques; antipyrétique, anti-inflammatoire, antioxydant et même anticancéreux. La calyciphylline B appartient à cette famille et possède un motif original comprenant sept stéréocentres adjacents, dont un stéréocentre quaternaire tout carbone, avec un échafaudage hexacyclique. Sa structure a été déterminée par données spectroscopiques, plus précisément par des techniques de RMN 2D. Malgré le peu d'information sur son activité biologique, sa synthèse représente sans le moindre doute un grand défi pour les chimistes organiciens. Le groupe de recherche du Prof. Hanessian a entrepris la synthèse totale de la calyciphylline B en 2010, laquelle est toujours en cours. Une nouvelle approche a été développée pour la préparation d'un intermédiaire azabicyclo[3.3.0]octane avancé. Ce mémoire résume les travaux de recherche de l'auteur sur les progrès réalisés pour la voie alternative élaborée par le groupe du prof. Hanessian. Le travail effectué comprend la formation d'un stéréocentre quaternaire, l'alkylation d'un énolate sur un triflate d'alkyle secondaire, une réduction diastéréosélective, une cyclisation réductrice ainsi qu'une oxydation de Wacker régiosélective. / The Daphniphyllum alkaloids constitute a broad class of natural products isolated from a genus of evergreen plants extensively used in traditional Chinese medicine. These alkaloids display an impressive range of biological activities, including antipyretic, anti-inflammatory, antioxidant, and even anticancer properties. Calyciphylline B is a structurally unique member of this family containing seven contiguous stereocenters including an all-carbon quaternary stereocenter with a fused-hexacyclic ring scaffold. Its structure was determined by spectroscopic methods, especially 2D NMR techniques. Despite the sparse availability of information on its biological activity, its synthesis is undoubtedly a great challenge for synthetic chemists. The research group of Prof. Hanessian embarked on the total synthesis of calyciphylline B in 2010 and the project is still ongoing. A new route was developed for the preparation of an advanced azabicyclo[3.3.0]octane intermediate. This thesis summarizes the research work of the author on the progress made for the synthetic route developed by the Hanessian group. The work done includes the formation of a quaternary stereocenter, alkylation of an enolate using a secondary alkyl triflate, diastereoselective reduction, reductive cyclization, and a regioselective Wacker oxidation.

Les alcaloïdes Daphniphyllum constituent une vaste famille de produits naturels isolés à partir de plantes à feuillage persistant couramment utilisés dans la médecine chinoise traditionnelle. Ils affichent une gamme impressionnante d'activités biologiques; antipyrétique, anti-inflammatoire, antioxydant et même anticancéreux. La calyciphylline B appartient à cette famille et possède un motif original comprenant sept stéréocentres adjacents, dont un stéréocentre quaternaire tout carbone, avec un échafaudage hexacyclique. Sa structure a été déterminée par données spectroscopiques, plus précisément par des techniques de RMN 2D. Malgré le peu d'information sur son activité biologique, sa synthèse représente sans le moindre doute un grand défi pour les chimistes organiciens. Le groupe de recherche du Prof. Hanessian a entrepris la synthèse totale de la calyciphylline B en 2010, laquelle est toujours en cours. Une nouvelle approche a été développée pour la préparation d'un intermédiaire azabicyclo[3.3.0]octane avancé. Ce mémoire résume les travaux de recherche de l'auteur sur les progrès réalisés pour la voie alternative élaborée par le groupe du prof. Hanessian. Le travail effectué comprend la formation d'un stéréocentre quaternaire, l'alkylation d'un énolate sur un triflate d'alkyle secondaire, une réduction diastéréosélective, une cyclisation réductrice ainsi qu'une oxydation de Wacker régiosélective. / The Daphniphyllum alkaloids constitute a broad class of natural products isolated from a genus of evergreen plants extensively used in traditional Chinese medicine. These alkaloids display an impressive range of biological activities, including antipyretic, anti-inflammatory, antioxidant, and even anticancer properties. Calyciphylline B is a structurally unique member of this family containing seven contiguous stereocenters including an all-carbon quaternary stereocenter with a fused-hexacyclic ring scaffold. Its structure was determined by spectroscopic methods, especially 2D NMR techniques. Despite the sparse availability of information on its biological activity, its synthesis is undoubtedly a great challenge for synthetic chemists. The research group of Prof. Hanessian embarked on the total synthesis of calyciphylline B in 2010 and the project is still ongoing. A new route was developed for the preparation of an advanced azabicyclo[3.3.0]octane intermediate. This thesis summarizes the research work of the author on the progress made for the synthetic route developed by the Hanessian group. The work done includes the formation of a quaternary stereocenter, alkylation of an enolate using a secondary alkyl triflate, diastereoselective reduction, reductive cyclization, and a regioselective Wacker oxidation.