Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Bis(2-arylaminoethyl)amines cannot be efficiently prepared by the obvious route from bis(2-chloroethyl)amine and anilines, as intramolecular cyclisation to piperazine is favoured over a second substitution to form the open triamine. A series of bis(2¬arylaminoethyl)amines was successfully prepared via a new and general route, the facile cleavage under acidic conditions of the corresponding bicyclic phosphoric triamides. In some cases, the resultant amines were functionalised further, ego yielding the trihydrochloride salts and the tri-N-acetylated derivatives. The base hydrolysis of the bicyclic phosphoric triamides in turn, may lead to the formation of interesting amino acids or zwitterions, as demonstrated for one of the derivatives. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

The synthesis and characterization of two new bulky N,P-monophosphaamidines (also known as C-aminophosphaalkenes) are described. These phosphorus analogues to amidines are shown to exhibit isomerism and tautomerism in solution that is characteristic tothe amidine functional group. In addition, the nature of the P=C-N system is examined using DFT techniques. Metal complexes of the title compounds with Group 6 metal carbonyls (L-M(CO)5, M=Cr,Mo,W) are also described. A new primary phosphane is reported that contains the sterically bulky, 2,6-diisoropylphenyl (Dip) group, along with mono and disilylated derivatives. Also included is the synthesis and characterization of a new bulky N,N',P-monophosphaguanidine. / xxxii, 280 leaves : ill. ; 28 cm.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2000. / Includes abstracts in Afrikaans and English. Includes bibliographical references (leaves 58-59).

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Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Cette thèse a été consacrée tout d'abord à l'étude du premier procédé domino méthylénation-hydrogénation des aldéhydes et des cétones. Ce processus repose sur la combinaison d'un réactif gem-bimétallique [CH2(ZnI)2] et un catalyseur de Wilkinson (ClRh(PPh3)3) en présence d'hydrogène moléculaire.L'étendue et les limites de cette réaction ont été explorées. Ensuite, l’étude de la réaction de semi-hydrogénation antid'alcynes par catalyse homogène a permis d’accéder de façon stéréosélective aux alcènes (E) correspondants. Cette réaction a été développée en utilisant des réactifs commerciaux et peu couteux : Zn0, ZnI2 et Cl2Pd(PPh3)2sous1 atmosphère d’hydrogène moléculaire. Ces conditions sont à ce jour les plus douces utilisées pour cette réaction.Finalement, la préparation d’imidates par condensation de furfurylamine sur une variété d’iminoester, et la synthèse d’amidines par la condensation d’amines primaires sur les imidates précedemment obtenus, ont été réalisées. L’évaluation de l’activité anti-oxydante des nouveaux composés formés (imidates et amidines) a donnée des résultats prometteurs. / During this research, the firstmethylenation-hydrogenation domino process of aldehydes and ketones has been studied. This process is based on the combination of a gem-bimetallic reagent [CH2(ZnI)2] and a Wilkinson catalyst (ClRh(PPh3)3). The scope and limitations of this reaction have been explored.Furthermore, the semi-hydrogenation antiof internal alkynes by homogeneous catalysis allowed stereoselective access to the corresponding alkenes (E). This reaction was developed using commercially available and low expensive reagents: Zn0, ZnI2 and Cl2Pd(PPh3)2under H2 atmosphere. The use of easy handle and soft conditions had been first described.Finally, two synthetic routes were used to prepare imidates and amidines. The first were obtained from furfurylamine and iminoesters, while amidines were prepared from the condensation of primary amines on previous imidates. Evaluation of the antioxidant activity of these compounds gave promising results.

Indiana University-Purdue University Indianapolis (IUPUI) / The DNA minor groove continues to be an important biological target in the development of anticancer, antiviral, and antimicrobial compounds. Among agents that target the minor groove, studies of well-established benzimidazole-based DNA binders such as Hoechst 33258 have made it clear that the benzimidazole-amidine portion of these molecules promotes an efficient, site-selective DNA association. Building on the beneficial attributes of existing benzimidazole-based DNA binding agents, a series of benzimidazole-amino acid conjugates was synthesized to investigate their DNA recognition and binding properties. In this series of compounds, the benzimidazole-amidine moiety was utilized as a core DNA “anchoring” element accompanied by different amino acids to provide structural diversity that may influence DNA binding affinity and site-selectivity. Single amino acid conjugates of benzimidazole-amidines were synthesized, as well as a series of conjugates containing 20 dipeptides with the general structure Xaa-Gly. These conjugates were synthesized through a solid-phase synthetic route building from a resin-bound amino acid (or dipeptide). The synthetic steps involved: (1) the coupling of 4-formylbenzoic acid to the resin-bound amino acid (via diisopropylcarbodiimide and hydroxybenzotriazole); followed by (2) introduction of a 3,4-diaminobenzamidoxime in the presence of 1,4-benzoquinone to construct the benzimidazole ring; and, finally, (3) reduction of the resin-bound amidoxime functionality to an amidine via treatment with 1M SnCl2•2H2O in DMF before cleavage of final product from the resin. The synthetic route developed and employed was simple and straightforward except for the final reduction that proved to be very arduous. All target compounds were obtained in good yield (based upon weight), averaging 73% mono-amino acid and 78% di-amino acid final compound upon cleavage from resin. Ultimately, the DNA binding activities of the amino acid-benzimidazole-amidine conjugates were analyzed using a fluorescent intercalator displacement (FID) assay and calf thymus DNA as a substrate. The relative DNA binding affinities of both the mono- and di-amino acid-benzimidazole-amidine conjugates were generally weaker than that of netropsin and distamycin with the dipeptide conjugates showing stronger binding affinities than the mono-amino acid conjugates. The dipeptide conjugates containing amino acids with positively charged side chains, Lys-Gly-BI-(+) and Arg-Gly-BI-(+), showed the strongest DNA binding affinities amongst all our synthesized conjugates.

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