This thesis describes investigations into tandem catalysed synthesis of polycyclic heteroatom containing molecules and the utilisation of high throughput screening (HTS) methodologies to identify active catalysts. Methodology for the high throughput screening of in situ generated metal complexes as catalysts was developed. UV spectroscopy and Capillary Electrophoresis (CE) were developed as effective methods of screening combinatorial arrays of complexes as catalysts. HTS methodologies were applied to the screening of in situ generated complexes as catalysts for the hydroamination of 2-(2-phenylethynyl)aniline. Two complexes were identified to be highly active hydroamination catalysts in acetone; the in situ combinations of [Rh(CO)2Cl]2/mesBIAN 38/NaBF4 and Ir(COD)Cl]2/NaBF4. Also identified in this work was the formation of the unusual N-(2-methylvinyl)-2-phenylindole catalysed by [IrCp*Cl2]2/NaBF4 from 2-(2-phenylethynyl)aniline via the incorporation of one molecule of acetone. Complexes of the type [Cp*MCl(N-N)][X] were synthesised (M = Rh(III) / Ir(III)), N-N= bpm 31, bim 32, dmbpm 61, bik 62, mesBIAN 38 and mesim-mim 63, X= Cl-, BF4-, [Cp*MCl3]-). Where N-N was bpm 31 or bim 32 and there was no alternate counterion present, bimetallic complexes formed containing the counterion X= [Cp*MCl3]-. The three dimensional, solid state, structures of the cationic fragments of the bimetallic complexes [Cp*MCl(N-N)][X] (M= Ir, X= [Cp*IrCl3]-, N-N= bpm 31 and bim 32; M= Rh, X= [Cp*RhCl3]-, N-N= bpm 31; M= Ir, X= BF4 -, N-N= bim 32, mesBIAN 38 and mesim-mim 63) are presented. Abstraction of the chloride, in complexes of the type [Cp*IrCl(N -N)]BF4, by AgBF4 created active catalysts in situ with the best catalyst in the series for the hydroamination of 2-(2-phenylethynyl)aniline [Cp*IrCl(mesBIAN)]BF4/AgBF4. Investigations performed into the synthesis of N-(2-methylvinyl)-2-phenylindole catalysed by [IrCp*Cl2]2/BF4- have shown that the most likely potential mechanism proceeds via the initial catalysed formation of the imine followed by metal promoted cyclisation. The isolation of the complex [IrCl2(2-(2-phenylethynyl)aniline)Cp*] and investigation into its reactivity showed it to be a potential reactive intermediate in the catalytic cycle. Investigation into catalysed C-C bond formation of N-propargylindole identified the in situ generated complex [Rh(CO)2Cl]2/PPh3 as a catalyst for the generation of pyrroloquinoline as a 1:1 mixture of regioisomers.

This thesis explores the synthesis and conformational behaviour of hexahydropyrimidines and related heterocycles, with particular emphasis on 5- hyrdohexahydropyrimidines. The conformational behaviour of these compounds was investigated using dynamic NMR spectroscopy, molecular modelling techniques and X-ray crystal structure analysis. The conformational behaviour of 5- hyrdohexahydropyrimidine, hexahydropyrimidine and their analogous oxygen compounds as well as a series of hexahydropyrimidines with various exocyclic substituents, were examined. The preferred conformations of all these compounds are attenuated by a combination of steric and electronic influences. These influences include intramolecular hydrogen bonding as well as anomeric and gauche interactions. The conformational behaviour of the selected seven membered benzodiazepine rings, which share structural characteristics with the six-membered 5- hyrdohexahydropyrimidines was also explored. The increased flexibility of the seven membered rings facilitates intramolecular hydrogen bonding, which in turn retards ring inversion in these systems / Doctor of Philosophy (PhD)

The pyrrolo[3,2,1-ij]quinolin-6-one ring system was synthesised from 3-aryl-4,6-dimethoxyindoles and 2,3-disubstituted-4,6-dimethoxyindoles. The reaction of 4,6-dimethoxyindoles under Friedel-Crafts or Vilsmeier-Haack acylation gave the 2- and 7-indolyldeoxybenzoins in good yield. Cyclisation of 7-indolyldeoxybenzoins with N,N-dimethylformamide dimethyl acetal as a one carbon reagent gave the pyrroloquinolin-6-ones in high yield. Reduction of pyrroloquinolin-6-ones with hydrogen gas and 10% palladium on carbon or lithium aluminium hydride yielded the dihydropyrroloquinolin-6-ones. Demethylation of pyrroloquinolin-6-ones with 48% hydrobromic acid in glacial acetic acid gave a mixture of the monohydroxy and dihydroxy analogues in high yield. The synthesis of quinolin-4-ones using the Conrad-Limpach method was attempted using three different cyclisation conditions such as Dowtherm A, polyphosphoric acid and a mixture of diphenyl ether and methanesulfonic acid. Quinolin-2-ones such as 4-methyl-3-aryl-, 3,4-diaryl- and 3-aryl-4-benzyl-5,7-dimethoxyquinolin-2-ones could be synthesised from either the N-phenylacetylaniline or the N-trifluoroacetyl aniline strategy. Attempted reduction of the quinolin-2-ones with standard metal hydride reagents was unsuccessful. However reduction was achieved via the conversion of quinolin-2-one to the corresponding 2-chloroquinoline followed by reaction of the chloroquinoline with zinc powder and glacial acetic acid to produce a novel, highly substituted quinoline system. Demethylation was successfully carried out with 48% hydrobromic acid in glacial acetic acid to give the trihydroxyquinolin-2-one in high yield. The reactions of 4-substituted-5,7-dimethoxyquinolin-2-ones and the corresponding 2-chloroquinolines as potential organic intermediates were explored. Facile formylation of both quinolin-2-ones and 2-chloroquinolines was observed under Vilsmeier-Haack conditions while acetylation was successful under Friedel-Crafts conditions using antimony (V) pentachloride as the Lewis acid. Further reaction of 8-formyl-quinolin-2-one with 1,2-diaminobenzene in N,N-dimethylformamide led to the formation of a new 8-(benzimidazolyl)-quinolin-2-one ring system. The quinolin-2-ones exhibited selective electrophilic substitution at the C8 position for a range of reactions. However, an unexpected nitration occurred at the C3 position for the 4-methoxy and 4-phenyl-5,7-dimethoxyquinolin-2-ones with good yields. A series of novel 4,6-hydroxylindoles was successfully synthesised from the corresponding methoxy analogues in high yield using anhydrous aluminium chloride. When 3-(4-bromophenyl)-4,6-dimethoxyindole was reacted with 48% hydrobromic acid in glacial acetic acid a 2,2?-indolylindoline dimer was formed. The 5,7-dihydroxyquinolin-2-ones were similarly synthesised in high yield using anhydrous aluminium chloride in chlorobenzene.

Thesis (M.S.)--Oregon Graduate Center, 1972.

Thesis (M.S.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 105-114). Also available on the World Wide Web.

Ph.d.

Thesis (Ph. D.)--University of Hong Kong, 1987.

Thesis (M. Phil.)--University of Hong Kong, 1986.

Thesis (M. Phil.)--University of Hong Kong, 1989.

published_or_final_version / Chemistry / Master / Master of Philosophy