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It has been found that by combining various borocations or neutral electrophilic boranes with a multitude of alkynes, interesting and often highly selective borylation reactivity is observed. The reactions can be loosely categorised as de-(elemento)boration of the alkyne, haloboration and carboboration. Direct alkyne de-(elemento)boration was achieved as both dehydroboration and desilylboration, generating a selection of borylated alkynes. Other examples of more complicated alkyne borylation were also observed, such as the boroamination of TMS-ethylene. Upon discovering that 2-N,N-dimethylaminopyridine ligated dichloro-boronium salt underwent selective 1,2-haloboration with a range of terminal alkynes, and that the dibromo-analogue could haloborate a limited number of internal alkynes, the more Lewis acidic borenium salt [Cl2B(2,6-lutidine)][AlCl4] was synthesised and reacted with a series of internal alkynes to give haloborated products. These included dialkyl and diaryl internal alkynes containing a range of functional groups including thioether, methoxyphenyl, vinyl and halide. Each proceeded with excellent stereo- and regio-selectivity, with the boron and the halide added mutually cis, and the regioselectivity determined by the electronically most stable form of the carbocation intermediate. The initial dihalovinyl borane products were esterified in-situ to provide the more stable pinacol boronate esters. The elementoboration method was expanded via modification of the borocations to include different transfer groups that, upon reaction with trimethylsilyl-substituted alkynes, underwent 1,1-carboboration, with migration of the TMS-group. This method also provided access to a small selection of borylated dienes, resulting from reactions with excess alkyne. It was also shown that some neutral boranes reacted analogously with certain TMS-alkynes, albeit with limitations on scope. In addition to this, two types of 1,2-carboboration were discovered. The first involved intercepting products from alkyne haloboration with a TMS-alkyne, undergoing a vinylboration to produce 1-boradiene products. The second was an example of an intermolecular trans carboboration, where the initially formed vinyl carbocation is intercepted by a thiophene.

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Despite their ubiquitous use, Pt(II) anti-cancer drugs still suffer from many issues such as off-drug target effects, renal and nephrotoxicity as well as acquired and intrinsic drug resistance. To obtain a better understanding of how to mitigate these deleterious effects can be mitigated we first must know all the targets of these drugs. Highlighted in this dissertation is previous work performed by groups exploring the localization of Pt in cells using fluorescence microscopy. While Pt drugs such as cisplatin contain no native fluorescence, a great deal of work has been done to covalently modify complexes with fluorescent tags. From studies using this technique, it been reported that Pt can target a number of compartments within the cell ranging from the nucleus to the cytoplasm. With each different derivative being observed in varied cell lines it becomes difficult to deconvolute a universal pattern to where Pt localizes, furthermore, the connected fluorophore could also bias Pt localization. To add general functionality and eliminate the bias of a pre-tethered fluorophore our lab has developed a number of different azide and alkyne-modified complexes that append a “reactive handle” to Pt compounds. This modification allows for use of the bioorthogonal azide-alkyne click reaction we are able to observe Pt localization after treatment. The focus of this work includes method development to conjugate a fluorophore to our Pt complexes in vitro and in cell cultures. We examined a number of different cell lines and observed frequent localization in the nucleolus of the cell. Also in this work is the development of methods to append multiple fluorophores to each Pt site to increase our ability to visualize these complexes in cells. Finally, we have also constructed a new Pt-azide that exhibits slower exchange kinetics due to a chelating exchangeable group. The use of this new complex will enable studies to determine whether changing the leaving group results in differential localization of Pt drugs in cells.

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No description available.

No description available.

No description available.