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.

Diversity in the fitness industry : a cross-case comparison /

This cross-case study explored the extent to which two fitness facilities were accommodating diversity with respect to age, ethnicity, gender, social class, sex-role socialization, and persons with a disability among both members and staflf. The sites were purposely chosen in a large city and a smaller city in order to provide as representative an example as possible of health clubs within a small sample population. The interview participants were selected by a combination of stratified, typical case, and snowball sampling strategies. . , .. , The intent of the exploration was a two-fold examination of diversity issues within both the membership and the staff of the organization. Data were collected and analysis was done using a triangulation method involving personal interviews, observations, and facility documentation. The results ofthe study showed that the members and staff at each facility were rather homogeneous in ethnicity, age, social class, physical ability, and physical appearance. From a membership standpoint, the environment of the sites presented the impression of being affordable only to the middle- and upper-middle classes, unwelcoming to the older, less fit, or overweight participant, economically exclusive for youth, and nonaccommodating for people with a disability. With respect to staff, the findings indicated that the fitness facilities purported to be team-oriented in theory, but were hierarchical in practice, with the major decision making being made by the male executives. The paper concludes with the recommendation that students must be given a practical toolkit for dealing with these issues in their postsecondary courses.

Greener Golf Operations: A Comparative Case Study of Ontario Golf Courses Engaged in Environmental Sustainability Initiatives

This research explored environmental sustainability (ES) initiatives at five top-ranked Ontario golf courses that were members of the Audubon Cooperative Sanctuary Program for Golf (ACSP). Research Questions: (1) How are golf courses adapting to safeguard the natural environment? (2) Why or why not are golf courses moving to ES? and (3) What are the arising barriers to ES in golf and how can they be overcome; what role does communication play? Overall, the research was framed with an adaptation of the dimensions of convergence by Houlihan (2012), including the motives, inputs, implementation, momentum, and impact. Additionally, impression management and message framing constructs were utilized to address the issue of communicating ES initiatives. Data collection involved in-depth interviews, observations, and unobtrusive document collection. Environmental aspects of the examination were guided by the Canadian Standards Association (CSA) Requirements and Guidance for Organizers of Sustainable Events and Sustainable Sport and Event Toolkit (SSET).

The Influence of Burnout Symptoms on the Relationship between Work-Life Balance and Self-Rated Health

The effects of stress at work are estimated to cost Canadian employers more than 20 billion dollars annually through absenteeism, sick leave and decreased productivity. Over the past two decades, Canadians have reported higher stress levels, increased work hours and more work performed outside of normal business hours. This work-life imbalance has far-reaching repercussions–affecting an employee’s performance as well as their health. Chronic exposure to these high levels of stress can also lead to burnout. The primary purpose of this study was to determine the magnitude in which burnout symptoms influence the relationship between work-life balance and self-rated health. The secondary purpose of this study was to determine if gender and age interactions exist in the relationship between burnout, work-life balance, and self-rated health. This cross-sectional study involved secondary analysis of 220 managers, workers and human service professionals who completed an Occupational Health Clinics for Ontario Workers’ Mental Injury Toolkit (MIT) survey for the launch of the MIT. The MIT survey is a modified form of the short version of the Copenhagen Psychosocial Questionnaire and includes expanded questioning around burnout, stress, sleep troubles, cognitive, and somatic symptoms. There were no significant differences in self-rated health based on a respondent’s gender or age, indicating that no interaction of gender and age would be required. Respondents with low self-rated health reported significantly higher burnout and work-life imbalance compared to those with high self-rated health. The regression analysis demonstrated that the magnitude in which burnout mediates the relationship between work-life balance and self-rated health was 96%. These findings support previous studies that associate high levels of work-life imbalance or burnout with poor self-rated health or health outcomes. In this study, the shared variance between work-life balance and burnout also supports recent efforts to redefine the context and causes of burnout to include non-work factors. Based on our findings, the potential exists for the development of workplace health promotion strategies that address maintaining a balance between work and home as they may improve employee health and reduce burnout.