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.

The new blockbuster film sequel : changing cultural and economic conditions within the film industry

Film sequels are a pervasive part of film consumption practices and have become an important part of the decision making process for Hollywood studios and producers. This thesis indicates that sequels are not homogenous groups of films, as they are often considered, but offer a variety of story construction and utilize a variety of production methods. Three types of blockbuster sequel sets are identified and discussed in this thesis. The Traditional Blockbuster Sequel Set, as exemplified by Back to the Future (1985, 1989, 1990) films, is the most conventional type of sequel set and capitalizes on the winning formula of the first film in the franchise. The MultiMedia Sequel Set, such as The Matrix (1999,2003) trilogy, allows the user/viewer to experience and consume the story as well as the world of the film through many different media. The Lord a/ the Rings (2001, 2002, 2003) set of films is an illustration of The Saga Sequel Set where plot lines are continuous over the entire franchise thus allowing the viewer to see the entire set as a unified work. The thesis also demonstrates how the blockbuster sequel sets, such as the Pirates a/ the Caribbean (2003, 2006, 2007) franchise, restructure the production process of the Hollywood film industry.

The role of motivational systems in community service involvement : initiating and sustaining factors and quality of experience /

Community service participation can have a positive impact on development, especially for youth. Although researchers have found positive outcomes, there has been a notable decline in youth participation over the past few years (Statistics Canada, 2000). Given the positive outcomes and current decline, it has been argued that youth should be encouraged to get involved in service activities. In the present study, quantitative and qualitative data were collected to determine factors that would help youth to initiate and sustain service, along with examining the quality of their experience. Eighty-two university undergraduate students (23 men), ranging in age from 17-20 years completed a 60-minute self-report questionnaire. Initiating and sustaining factors, motivational systems (similar to approach and avoidance dimensions), activity dimensions {Structure, Supportive Social Environment), quality of experience {Positive, Stress-Challenge), and future intention to participate in community service were measured. Eight participants also completed a 20-minute telephone interview to complement and expand on the quantitative data collected. Some initiating and sustaining factors were specific to individuals higher on the avoidance dimension, while others were relevant to those higher on the approach dimension. Several factors also were important to individuals regardless of their motivational system orientation. Positive quality of experience was related positively to experiencing a supportive social environment. In addition, women rated their community service as more positive than did men. A predicted interaction between the avoidance dimension and Structure in predicting positive quality of experience was not supported; however, positive quality of experience was predicted by the interaction of the approach dimension and Structure. A tested interaction between the avoidance dimension and Supportive Social Environment in predicting positive quality of experience was not supported. Similarly, a predicted interaction between the approach dimension and Supportive Social Environment in predicting positive experience quality was not supported. However, Supportive Social Environment was positively related to positive quality of experience. No support was found for a mediational role for positive quality of experience or stress-challenge quality of experience in exploring the relation between motivational orientation and fiiture intention to engage in service activities. The results of this study suggest that participating in a service environment that is supportive and provides the opportunity for social interactions with others would promote positive quality of experience and help youth sustain involvement. Thus, to help youth have positive experiences and to remain active in service, it is important for service agencies to promote these types of environments. In addition, some initiating and sustaining factors were specific to youth higher on the avoidance dimension and some were relevant to youth higher on the approach dimension. Therefore, service agencies may need to consider using different recruitment and retention strategies, depending on the type of youth they wish to recruit.

An inquiry into the barriers to participation within the fitness industry for people living with mobility challenges

This qualitative study was designed to inquire about the barriers to participation within the fitness industry for people living with mobility challenges. i\n examination of the insights, stolies~ and experiences with barriers through interviews gi ven by 4 people living with mobility challenges (PMC) formed the core of the research. An analysis of the interviews from the 4 PMC informants was performed at t\\/O levels. First, a content analysis served to identify general and specific categories related to barrier issues within various fitness environments. Secondly, in-depth thematic analyses of the entries related to the insights and stories from the 4 informants which emerged from the content analysis of the data gave rise to fi ve thematic statements. From the thematic statements a fitness industry awareness protocol was created in the fonn of a statement response questionnaire. The protocol, which was given to 4 fitness assessors/trainers, \vas used to provide a snapshot of the fitness industry's readiness to work vvith disability. Throughout the process, the four PNIC informants formed a collaborati vely involved group of coresearchers, adding their voices to the narrative of the fitness-barrier experience. The result of the study suggests that barriers to participation within the fitness industry for PMC exist in various forms and levels of severity. The results also suggest that the fitness industry needs to better prepare their people and environment for working with people with physical disabilities, such as PMC, and provide a more open and positi ve environment for participation. Within the context of any fitness-related environment, recognizing that barriers to participation do exist, and acknowledging and accepting people with disabilities for who they are as indi viduals, will serve to develop a relationship where fitness practitioners and people with disabilities can work towards creating an inviting, inclusive, accessible, and barrier-free fitness environment for all.

Examining and describing professional development and continuing education in the personal training and fitness industry : sites and issues of disconnect

The following phenomenologically oriented study examines and describes the relevance and effectiveness of professional development and continuing education programs for real-world situations of personal trainers. The participants were personal trainers, facility managers, and persons involved in the accreditation process. Data collection took place in 3 phases. The first phase consisted of the participants completing the PUMP Questionnaire, followed by focus groups with personal trainers and interviews with managers. The study's 3 data sets required reduction via a content analysis by question, content analysis by existential categories, and further thematic analysis using the lived relation existential dimension. The discussion contains the salient sites and issues of disconnect between clients, personal trainers, and facility managers and how they might affect the personal training experience. The intergenerational disconnect emphasized between Boomers as clients and Millennials as personal trainers requires further exploration and dialogue and underscores the need for different approaches to content and delivery of professional development and continuing education experiences for personal trainers and managers of fitness facilities.

Insights Into the Remembered Educational Experiences of Male Caribbean Immigrants to Canada: Literacy and Identity in the Canadian Classroom

Abstract Past research has addressed the issue of male underachievement in literacy as an issue of global concern. This qualitative study focused on one subgroup of males which the literature highlighted as most at risk of educational underachievement in the Canadian educational landscape: male Caribbean immigrants to Canada. The research questions that framed the study sought to gain insight into the educational experiences of this group of learners so that ways through which their literacy achievement as measured by academic performance and classroom engagement could be projected. New literacy studies view literacy as socioculturally bound in social, institutional, and cultural relationships (Gee 1996). Literacy can therefore be thought of as an extension of self that Lankshear and Knobel (2006) assert is always connected to social identities. Central to the research questions as a result of this perspective was the discovery of the ideologies of reading held by the participants and their connections to literacy practice. Supplementary questions delved into socially valued literacy practices and ways in which learners saw themselves as Black males reflected in the Canadian educational framework. In this qualitative study with an interview design, data were collected through individual semistructured interviews with the 4 participants and through a focus group session with all the participants. The findings depicted that identity, interests, and ideologies of reading all influenced the literacy practices and engagement of Caribbean males. The findings documented are valuable as they provide a fresh perspective surrounding the educational experiences of the male Caribbean learner and can present insights which can lead to enhanced academic engagement and improved student achievement for this group of learners.