Single electron transfer (SET) mechanisms are becoming ubiquitous in modern organic chemistry. However, it is often difficult to distinguish SET mechanisms from polar mechanisms. Kinetics, products and product distributions, and response to perturbation in solvent and substituents are often identical between the two mechanisms. Detection techniques such as EPR, CIDNP, and UV absorption can often detect "blind" pathways and thus cannot provide unambiguous evidence regarding the true mechanism of interest. In recent years mechanistic probes have been developed which can test for single electron transfer in the mechanism of interest in a more unambiguous manner, although a given probe is often applicable to a narrower range of reactions. In this work 1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one (6) is presented as a new "hypersensitive" probe for single electron transfer to conjugated carbonyl compounds. This new probe functions in a rather unique fashion, allowing interpretation of the mechanism at work on the basis of the regiochemistry of spirocyclic ring opening. This "regiodifferentiation" based probe was studied with a variety of nucleophiles (particularly Grignard reagents) and has been found to be effective in differentiating SET from polar processes, although surprising results indicative of polar pathways in the case of reaction of 6 with Grignard reagents other than methyl Grignard were found. Additional insight into the mechanism of the reaction of Grignard reagents with conjugated ketones is also presented. / Master of Science

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<p> Three cholic acid derived chelating reagents were synthesized. They were synthesized by the attachment of existing chelating ligands onto the side chain of cholic acid via a spacer chain which connects cholic acid and chelate. The incorporation of the ligands EDTA, DTPA and DHPTA onto suitable cholic acid derivatives was performed to produce the respective cholic acid derivatives: cholic acid -EDTA, cholic acid-DTPA, and cholic acid-DHPTA. The synthesis of a fourth chelating reagent was attempted by attaching HEDTA onto the cholic acid side chain but was unsuccessful . A complete account of the three syntheses and one partial synthesis are outlined in this thesis. </p> / Thesis / Master of Science (MSc)

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An azavinamidium salt, [3-(Dimethylamino)-2-azaprop-2-en-l-ylidene] dimethylammonium chloride was reacted with primary amides, esters containing an ╬▒-methylene group and Grignard reagents. The reaction of this azavinamidium salt with amides and esters produced respectively, acyl amidines and enamino esters. Both of these products were produced in high yields by using relatively mild conditions. Reaction of the salt with Grignard reagents resulted in a novel synthesis of aldehydes. This aldehyde synthesis was shown to be of general utility and to proceed in high yields.

This work is a study of the product formed by the reaction of magnesium on bromobenzene in the absence of a solvent, and the results of hydrolysing this product. 1. By refluxing bromo benzene and magnesium, reaction takes place to form phenylmagnesium bromide, di phenyl and terphenyl. The yield of phenyl magnesium bromide was found to be 24-30 %. 2. The quantity of di phenyl formed is several times the runount formed when ether is used as a solvent. 3. Terphenyl was isolated from this reaction. / M.S.