Thesis presented to the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY for the degree of MASTER OF TECHNOLOGY Department of Chemistry, Cape Peninsula University of Technology, Cape Town Campus, Zonnebloem, October 2013 / In this thesis, the complexation behaviour of the host compounds, 1,1’-binaphthyl- 2,2’-dicarboxylic acid (BNDA) and 1,1’-binaphthyl-2,2’-diol (BINOL) were investigated. These hosts are large, bulky and scissor shaped; they contain functionalities to selectively interact with other molecules. A series of small organic compounds, particularly amines, were used in the preparation of the complexes. BNDA formed three complexes with acyclic amines, two complexes with the cyclic amines and two complexes with a racemic amine in different solvents. All the complexes formed were salts. The amines used were diethylamine, di-nbutylamine, cyclohexylamine, dicyclohexylamine, and sec-butylamine. For the studies with the acyclic amines and cyclic amines, crystals were grown in methanol as a co-solvent. Similar experiments were conducted with BINOL. Successful complexation only occurred with cyclohexylamine and dicyclohexylamine respectively. An amine host, 1,1’-binaphthyl-2,2’- diamine (BINDIA) was also considered with acidic and amide guests to extend the study of the binaphthyl derivatives, but from the array of guests used, the host only formed an inclusion compound with dimethylacetamide (DMA). The structures of all the complexes were elucidated using single crystal X-ray diffraction. Thermal analysis was performed in order to determine the thermal stability of the complexes, including techniques such as thermogravimetry, differential scanning calorimetry and hot stage microscopy. The kinetics of desolvation was investigated for some of the complexes.

Les ligands de carbènes N-hétérocycliques (NHC) qui possèdent une symétrie C1 attirent beaucoup l’attention dans la littérature. Le présent projet de recherche propose de synthétiser une nouvelle série de ligands NHC C1-symétriques avec deux groupements N-alkyles qui exploitent un relais chiral. Un protocole modulaire et efficace pour la synthèse des sels d’imidazolium chiraux qui servent comme préligands pour les NHC a été développé. Quelques-uns de ces nouveaux ligands ont été installés sur le cuivre et de l’or, créant de nouveaux complexes chiraux. Les nouveaux complexes à base de cuivre ont été évalués comme catalyseurs pour le couplage oxydatif de 2-naphthols. Les ligands C1-symmétriques ont fourni des meilleurs rendements que les ligands C2-symmétriques. Au cours de l’optimisation, des additifs ont été évalués; les additifs à base de pyridine ont fourni des énantiosélectivités modérées tandis que les additifs à base de malonate ont donné des meilleurs rendements de la réaction de couplage oxydatif. Ultérieurement, les additifs à base de malonate ont été appliqués envers l’hétérocouplage de 2-naphthols. Le partenaire de couplage qui est riche en électrons est normalement en grand excès à cause de sa tendance à dégrader. Avec le bénéfice de l’additif, les deux partenaires de couplage peuvent être utilisés dans des quantités équivalentes. La découverte de l’effet des additifs a permis le développement d’un protocole général pour l’hétérocouplage de 2-naphthols. / A new class of C1-symmetric N-heterocyclic carbene (NHC) ligands has been developed. The new ligands exploit a biaryl methyne as a chiral relay, and an N-methyl group as a reactivity controlling element. The precursors for the new ligands were synthesized via a modular scheme that allows for facile diversification. Several of the new ligands were installed onto both copper and gold, generating mono N-heterocyclic carbene transition metal complexes. The new C1-symmetric copper complexes were tested as catalysts for the synthesis of binaphthols via the oxidative coupling of electron poor 2-naphthols. The new C1-symmetric ligands afforded higher yields than their C2-symmetric counterparts. During the course of the optimization, small molecule additives were found to modulate the reactivity of the copper catalyst. Pyridine additives, such as 2-picoline, were found to induce low to moderate enantioselectivity in the oxidative coupling reaction, while diethylmalonate was found to improve the reaction yield without affecting the selectivity. The malonate additive was employed in the catalytic oxidative heterocoupling of electronically dissimilar 2-naphthols. The electron-rich coupling partner is normally added in a large excess due to its tendency to degrade. When the malonate additive is used, the coupling partners can be used in equimolar quantities. The discovery resulted in the development of a general protocol for the additive assisted aerobic oxidative heterocoupling of electronically dissimilar 2-naphthols.