No description available.

The primary goal of this study is to develop novel metal catalyzed multicomponent reaction methods to generate imidazoles and their derivatives. This is directed towards the assembly of poly-substituted imidazoles, imidazolones and imidazole-containing pi-conjugated polymers. These products are generated in one-pot from such basic components as imines, acid chlorides, carbon monoxide, and/or organostannanes, via the use of palladium catalysis. / In Chapter 2, the design of a new palladium catalyzed synthesis of highly substituted imidazoles from imines and acid chlorides is described. This reaction involves the palladium catalyzed generation of 1, 3-oxazolium-5-oxides (Munchnones); which are trapped with N-tosyl substituted imines via a 1, 3 dipolar cycloaddition reaction to form the final products. Overall, this provides a one step method to assemble imidazoles from imines and acid chlorides with excellent regiochemical control. The versatility of this process is demonstrated by the assembly of diversely substituted imidazoles, including those with aryl, alkyl, heterocyclic and vinyl substituents. / Chapter 3 describes a new, palladium catalyzed, five component coupling of imines, chloroformates, organotin reagents, carbon monoxide and ammonium acetate to form imidazolones. The key step in this process is the efficient formation of ketocarbamates via the carbonylative cross coupling type reaction of imines, chloroformates and organostannanes. These products can be easily converted into imidazolones via a cyclocondensation with ammonium acetate. / The synthesis of pi-conjugated imidazole-containing polymers is described in Chapter 4. This process is designed based upon our previous studies on palladium catalyzed multicomponent synthesis of imidazoles, developed in Chapter 2. It is shown that bifunctional monomers such as di-imines, di-acid chlorides and di-N-tosylimines can be coupled together to assemble pi-conjugated imidazole-containing oligomers and polymers utilizing this same palladium catalyzed reaction. This approach was used to create a novel library of conjugated imidazole polymers. By modifying the substituents on the polymer structures, the UV-vis absorbance and fluorescence excitation/emission spectra of these compounds are varied over a range of 150 nm. / In Chapter 5, the palladium catalyzed multicomponent polymerization is discussed in more detail. This includes the analysis of the end groups on the polymer backbone, as well as mechanistic studies into how the polymerization is terminated. These results suggest that the sulfinate anion liberated upon N-tosylimine cycloaddition may be non-innocent in this polymerization, and its presence could lead to termination of the growing polymer chain.

No description available.

The overall objective of this study was the optimization of a model enzymatic system in organic solvent media for the biosynthesis of selected phenolic lipid compounds. The model enzymatic system consisted of cinnamic acid and oleyl alcohol as substrates using commercial immobilized lipase (Novozym 435) from Candida antarctica. The experimental findings showed that an increase in the hydrophobicity of the solvent mixture and a decrease in the aw values of the reaction medium increased the initial enzymatic activity and bioconversion yield; the use of an iso-octane and butanone solvent mixture (85:15, v/v) and an initial aw of 0.05 resulted in an initial enzymatic activity of 192.7 nmol product/g enzyme/min and a corresponding bioconversion yield of 95.3% after a 16-day reaction period.

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Abstract available in pdf file.

The synthesis of 7-N-acetyl-3'-demethyllavendamycin propyl ester (61 ), 7-N-butr-3'-demethyllavendamycin amide of N,N-dimethylethylenediamine (62), 7-N-acetyllavendamycin butyl amide (64), 7-N- acetyllavendamycin amide of ethanolamine (63) are described. Incorporation of the Pictet-Spengler condensation of 7acetamido-2-formylquinoline-5, 8-dione (32) or 7-butyramido-2-formylquinoline-5, 8dione (7) with tryptophan propyl ester (65), L-tryptophan amide of N, N dimethylethylenediamine (66), f3-methyltryptophan butyl amide (68), or methyltryptophan amide of ethanolamine (67) in xylene afforded four lavendamycin analogs.Aldehydes 32, 74 and 86 were prepared according to the following general procedure. Nitration of 8-hydroxy-2-methylquinoline (69) yielded 8-hydroxy-2-methyl - 5,7-dinitroquinoline (29). Compound 29 was then hydrogenated and acylated with acetic anhydride or butyric anhydride or 2-furoyl chloride followed by hydrolysis to yield 5,7diacetamido-8-hydroxy-2-methylquinoline (75) or 5,7- dibutyramido-8- hydroxy-2methylquinoline (73) or 5,7-difuroylamino-8-hydroxy-2- methylquinoline (84). Compounds 75 and 73 and 84 were oxidized by potassium dichromate to give the corresponding 5,8-diones 31 or 72 or 85. Treatment of 31 or 72 or 85 with selenium dioxide in refluxing 1,4-dioxane afforded compounds 32 and 74 and 86, respectively.Tryptophan propyl ester (65) was synthesized via a Fischer esterification of Ltryptophan with propyl alcohol saturated with hydrogen chloride. Compounds 66, 67, 68, 76, 77, 78, 79, and 80 were synthesized via the conversion of esters to amides with dimethylaluminum amides. Tryptophan methyl ester (23) and (3-methyltryptophan methylester (11) were treated with premixed trimethylaluminum and primary amines and refluxed to afford the desired tryptophan and (3-methyltryptophan amides.The structures of the novel compounds 61, 62, 63, 64, 66, 67, 68, 76, 77, 78, 79, 80, were confirmed through 1H NMR, IR, EIMS, and HRMS. Elemental analyses of Compounds 66, 68, 76, 77, 78 and 80 were also included. 1H NMR and IR for known compounds 29, 30, 31, 32, 71, 73, 74, 75, 84, 85, 86 were provided also. / Department of Chemistry

The Knoevenagel reaction is defined by the condensation of an aldehyde or ketone with a carbon nucleophile produced by the deprotonation of a methylene species whose acidity is dramatically increased by bonds to strongly electron withdrawing groups. Previously, our group developed an effective one-pot method for the preparation of 4H-chromenes using sodium borohydride reduction of the cyclized intermediates formed by the Knoevenagel condensation of malononitrile with salicylaldehydes in aqueous ethanol. In this study we outline the extension of these strategies to include 2’-hydoxyphenylketones as the starting material. Many of these compounds are also unique and were prepared by Friedel-Crafts acylation of phenols with acyl chlorides and/or Fries Rearrangement of the corresponding phenyl ester. The objective of this project has been to expand the application of the methods optimized in our lab for the simple and efficient formation of carbon-carbon bonds via the selective reduction of the alkylidene portion of the Knoevenagel reaction products. These methods have allowed for the production of several important classes of natural product-like compounds. Specifically, in this investigation, we have adapted these methods to the production of various 4-alkyl and 4-aryl substituted 3-amino-2-cyano-4H-chromenes. These types of molecules exhibit diverse pharmacological activity and have been shown to be potentially useful for the treatment of various diseases. A subset of the synthesized compounds will be submitted to Eli Lilly through their PD2 program. Further variation of substrates included the reaction of salicylaldehydes with ethyl cyanoacetate or cyanoacetamide which provided products unreported in the literature. Reactions with cyanoacetates gave the expected 3-carboethoxy(ester) functionalized 4H-chromene compounds. Products from cyanoacetamide were found to occur in open rather than cyclized forms. / Introduction and background literature -- Synthesis of 2'-hydroxyphenylketones -- Synthesis of 2-amino-3-cyano-4H-chromenes -- One pot method applied to salicylaldehydes with ethylcyanoacetate or cyanoacetamide. / Department of Chemistry

A powerful new one-pot method has been developed for the reductive alkylation of malononitrile with aromatic aldehydes. This new procedure has vastly improved the yield and efficiency and increased the scope for the aromatic aldehydes. Incorporating water as the catalyst in ethanol for the condensation step allows stoichiometric amounts of malononitrile and aldehyde to be employed. After dilution and cooling the reduction step takes place quickly and efficiently with sodium borohydride to give monosubstituted malononitriles.The product from the reductive alkylation of malononitrile with 2-quinolinecarboxaldehyde quickly rearranges to a novel indolizine on silica gel or with heat, while alkylation of the monosubstituted derivative provides an unsymmetrically disubstituted malononitrile.We have also investigated this improved one-pot reductive alkylation using various 2-hydroxybenzaldehydes where intramolecular cyclization occurs following the condensation step and various 2-amino-3-cyano-4H-chromenes are formed. / Department of Chemistry

Access to abstract permanently restricted to Ball State community only. / Access to thesis permanently restricted to Ball State community only. / Department of Biology