Thesis (Ph. D.)--University of Wisconsin--Madison, 1958. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.: leaves 82-84.

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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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.

L’addition nucléophile des réactifs de Grignard sur les nitriles conduit généralement aux cétones après hydrolyse acide. La double addition, menant à des carbinamines tertiaires après traitement, est beaucoup plus difficile et ne s’effectue habituellement qu’avec les organomagnésiens allyliques. Dans ce contexte, nous avons découvert que les organomagnésiens peuvent effectuer une double addition sur la fonction nitrile des acylcyanhydrines, pour fournir des hydroxyamides. Cette réaction est originale par le fait qu’une large gamme d’organomagnésiens peut être utilisée, dans des conditions particulièrement douces. Cette réaction a été appliquée à la synthèse de différents acides α-aminés α,α-disubstitués, par oxydation de la fonction alcool et hydrolyse du motif amide. La divinylglycine a notamment pu être préparée avec un bon rendement. L’addition successive de deux organomagnésiens différents a aussi pu être réalisée, après optimisation des conditions de réaction, pour accéder à des hydroxyamides disymétriques, précurseurs d’acides aminés quaternaires chiraux. Enfin, l’addition des réactifs de Grignard sur les 3-cyano iminocoumarines N-éthoxycarbonylées a été étudiée. Malgré la présence de nombreux sites électrophiles, la réaction est très chimiosélective, et des chromènes originaux substitués en position 4 ont été obtenus. Les propriétés antifongiques et antibactériennes de ces derniers ont été évaluées. / The nucleophilic addition of Grignard reagents on nitriles generally leads to ketones after acidic hydrolysis. The double addition, providing tertiary carbinamines after work-up, is more difficult and usually occurs only with allylic Grignard reagents. In this context, we discovered that Grignard reagents can perform a double addition on the nitrile function of acyl cyanohydrins, to provide hydroxyamides. This reaction is original by the fact that a wide range of Grignard reagents can be used, in particularly mild conditions. This reaction has been applied to the synthesis of different α,α-disubstituted α-aminoacids, by oxidation of the alcohol functionality and hydrolysis of the amide moiety. Especially, divinylglycine has been prepared in good yield. The successive addition of two different Grignard reagents was also carried out, after optimization of reaction conditions, to access unsymmetrical hydroxyamides, which are precursors of chiral quaternary aminoacids. Finally, the addition of the Grignard reagents on N-ethoxycarbonyl 3-cyano-iminocoumarines was studied. Despite the presence of several electrophilic centers, the reaction is highly chemoselective, and novel chromenes displaying substituent on position 4 were obtained. The antifungal and antibacterial properties of these compounds have been evaluated.

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Techn. Univ., Diss., 2007--Darmstadt

Thesis advisor: Shih-Yuan . Liu / Chapter 1. Use of boron as a pharmacophore is as growing but still underdeveloped strategy for expanding chemical space in biomedical research. In addition to more established methods of incorporating boron in drug development, an attractive and emerging method of introducing boron into biologically active compounds is through boron-nitrogen containing heterocycles. In particular, the Liu group has focused on exploring the interactions of monocyclic 1,2-azaborines in biological space. In order to install complicated chemical functionality needed for further studies, methods for late stage functionalization of 1,2-azaborines must be developed. Described herein is a method for functionalizing 1,2-azaborine at the C3- and C5-positions, with bromine and iodine handles, respectively. Chapter 2. Described is the application of the turbo Grignard reaction to 1,2-azaborines bearing a B–Cl bond. The reaction utilizes iPrMgCl·LiCl to form aryl carbon nucleophiles and is tolerant of sensitive functional groups such as nitriles and esters. Development of the reaction obviates the need to use toxic organotin reagents to install aryl groups at the B-position that bear sensitive, electrophilic functionalities. / Thesis (MS) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

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