Modifications to the Suzuki reaction and mechanistic insights on the NBS mediated cleavage of benzylidene acetals /

One of the most challenging tasks for a synthetic organic chemist today, is the development of chemo, regio, and stereoselective methodologies toward the total synthesis of macromolecules. r . The objective of my thesis was to develop methodologies towards this end. The first part of my project was to develop highly functionalized chirons from D-glucose, a cheap, chiral starting material, to be utilized in this capacity. The second part of the project dealt with modifying the carbon-carbon bond forming Suzuki reaction, which is utilized quite often as a means of combining molecular sub units in total synthesis applications. As previously stated the first area of the project was to develop high value chirons from D-glucose, but the mechanism of their formation was also investigated. The free radical initiated oxidative fragmentation of benzylidene acetals was investigated through the use of several test-case substrates in order to unravel the possible mechanistic pathways. This was performed by reacting the different acetals with N-bromosuccinimide and benzoyl peroxide in chlorobenzene at 70^C in all cases. Of the three mechanistic pathways discussed in the literature, it was determined, from the various reaction products obtained, that the fragmentation of the initial benzylic radical does not occur spontaneously but rather, oxidation proceeds to give the benzyl bromide, which then fragments via a polar pathway. It was also discovered that the regioselectivity of the fragmentation step could be altered through incorporation of an allylic system into the benzylidene acetal. This allows for the acquisition of a new set of densely functionalized. chiral, valuable synthetic intermediates in only a few steps and in high yields from a-Dglucose. The second part of the project was the utilization of the phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) as an efficient reusable medium for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts of water and toluene using potassium phosphate and 1% Pd2(dba)3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and afforded complete conversion within 1 hour at 50 ^C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70 ^C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system in which the top hexane phase contained the biaryl products, the palladium catalyst remained fully dissolved in the central THPC layer, while the inorganic salts were extracted into the lower aqueous phase. The catalyst was then recycled by removing the top and bottom layers and adding the reagents to the ionic liquid which was heated again at 50 ^C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences.

Niagara alternative food projects : networks, discourses and nature /

This thesis undertakes an exploration of the nature of alternative food projects in Niagara. A review of various theoretical approaches to the study of food and agriculture, suggests that actor-network theory offers the most useful lens through which to understand these projects. In particular, actor-network theory facilitates non-dualistic theorisations of power and scale and a commitment to the inclusion of non-humans in the 'social' sciences. The research is based on 19 in-depth interviews with actors involved in various urban and rural projects including community supported agriculture, community gardens, chefs using local seasonal food, a winery that grows organically, the good food box, a value-added small business, and organic producers. The analysis consists of four themes. The first analytical section pays special attention to the prominence of agri-tourism in Niagara, and examines the ways in which the projects in the sample interact with agri-tourist networks. In the second section the discussion focuses on the discourses and practices of resistance among Niagara alternative food actors. The participants' interviews suggest there are more discourses of resistance toward agri-tourist than toward dominant food networks. The third section questions commodity chain theorisations of alternative food projects. In particular, this section shows how the inclusion of non-human actors in an analysis confounds conceptualisations of 'short' and 'local' chains. The final analytical section assesses relations of power in Niagara alternative food projects. Three important conclusions arise from this research. First, Niagara alternative food projects cannot be conceptualised as operating at the 'local' scale. Broadening the scope of analysis to include non-human actors, it becomes apparent that these projects actually draw on a variety of extra-local actors. They are at once local and global. Second, the projects in this sample are simultaneously part of alternative, dominant and agri-tourist networks. While Niagara alternative food projects do perform many of the roles characteristic of alternative food systems, they are also involved in practices of development, business, and class distinction. Thus, alternative food networks should not be understood as separate from and in direct opposition to dominant food networks. Despite the second conclusion, this research determines that Niagara alternative food projects have made significant strides in the reworking of power. The projects represented in this thesis do engage in resistant practices and are associated with increased levels ofjustice.