The versatility and utilization of phosphorus based compounds in classic carbon-carbon bond forming and esterification reactions

The phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) has been employed as an efficient reusable media 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 ofwater and toluene (single phase) using potassium phosphate and 1% Pd2(dba)3'CHCI3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and were all complete 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, from which the catalyst was then recycled by removing the top (hexanes) and bottom (aqueous) 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. IL ESTERIFICATIONREACTION A new class oftrialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence oftriethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and stenc nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.

Half-sandwich Complexes of Ruthenium; Synthesis and Application to Catalysis

This thesis describes syntheses and catalytic reactivity of several half-sandwich complexes of ruthenium. The neutral ruthenium trihydride complex, Cp(PPri3)RuH3(1), can efficiently catalyse the H/D exchange reaction between various organic substrates and deuterium sources, such as benzene-d6. Moreover, the H/D exchange reactions of polar substrates were also observed in D2O, which is the most attractive deuterium source due to its low cost and low toxicity. Importantly, the H/D exchange under catalytic conditions was achieved not only in aromatic compounds but also in substituted liphatic compounds. Interestingly, in the case of alkanes and alkyl chains, highly selective deuterium incorporation in the terminal methyl positions was observed. It was discovered that the methylene units are engaged in exchange only if the molecule contains a donating functional group, such as O-and N-donors, C=C double bonds, arenes and CH3. The cationic half-sandwich ruthenium complex [Cp(PPri3)Ru(CH3CN)2]+(2) catalyses the chemoselective mono-addition of HSiMe2Ph to pyridine derivatives to selectively give the 1,4-regiospecific, N-silylated products. An ionic hydrosilylation mechanismis suggested based on the experiments. To support this mechanistic proposal, kinetic studies under catalytic conditions were performed. Also, the 1,4-regioselective mono-hydrosilylation of nitrogen containing compounds such as phenanthroline, quinoline and acridine can be achieved with the related Cp*complex [Cp*(phen)Ru(CH3CN)]+(3) (phen = 1,10-phenanthroline) and HSiMe2Ph under mild conditions. The cationic ruthenium complex 2 can also be used as an efficient catalyst for transfer hydrogenation of various organic substrates including carbonyls, imines, nitriles and esters. Secondary alcohols, amines, N-isopropylidene amines and ether compounds can be obtained in moderate to high yields. In addition, other ruthenium complexes, 1,3 and [Cp*(PPri3)Ru(CH3CN)2]+(4), can catalyse transfer hydrogenation of carbonyls although the reactions were sluggish compared to the ones of 2. The possible intermediate, Cp(PPri3)Ru(CH3CN)(H), was characterized by NMR at low temperature and the kinetic studies for the transfer hydrogenation of acetophenone were performed. Recently, chemoselective reduction of acid chlorides to aldehydes catalysed by the complex 2 was reported. To extend the catalytic reactivity of 2, reduction of iminoyl chlorides, which can be readily obtained from secondary amides, to the corresponding imines and aldehydes was investigated. Various substituted iminoyl chlorides were converted into the imines and aldehydes under mild conditions and several products were isolated with moderate yields.

Lipase-Mediated Enzymatic Catalysis For The Synthesis of New Chiral Polymers

Immobilized lipase B from Candida antarctica (N435) was investigated as a potential biocatalyst to generate silicone-based chiral polymers from monomers derived from the enzymatic dihydroxylation of bromobenzene. Several conditions and parameters have been investigated for this purpose and lipase transesterification preference to each of the free secondary alcohols in the chiral monomers was documented. The N435 was challenged with a series of substrates where the free alcohol moieties were systematically protected in order to study the substrate preference(s) for the transesterification reactions.

The challenges and successful strategies of secondary school administrators /

This study presents information gathered during personal interviews in the area of challenges that administrators have faced in their careers, and the strategies they have found to be successful in meeting those challenges. This research is a qualitative study, using an inductive approach. Five participants were chosen, based on convenience sampling, with semi-structured interviews that were audio recorded. The theoretical research found that school violence and stafS'school morale were key challenges facing administrators, with a variety of approaches suggested to foster success in meeting those challenges. Some of these approaches included knowledge, team work, an ethic of care, and having a school vision. From the interviews it became clear that the challenges administrators faced included those posed by students, including disciplinary issues, those posed by adults and those posed by government changes in education. In regards to strategies for success, the interviews revealed three key concepts that were emphasized as vital. These were the assets of craft knowledge (experience), collegiality, and the use of other professional resources and educators.

Evaluating three self-help smoking cessation interventions for post-secondary smokers : a randomized controlled trial on six Ontario campuses

Objective. Smoking prevalence is highest among the young adult cohort. Postsecondary students are no exception. Although many students intend to quit smoking, no research has established what methods best promote reductions in, or complete abstinence from smoking. This randomized controlled trial examined the effectiveness of three self-help smoking cessation interventions. Method. On six post-secondary campuses, 483 smokers who voluntarily accessed Leave The Pack Behind (a tobacco control initiative) were randomly assigned to one of three smoking cessation interventions: One Step At A Time (a 2-booklet, *gold standard' program for adults); Smoke|Quit (a newly-developed 2-booklet program for young adult students); and usual care (a 'Quit Kit' containing a booklet on stress management, information about pharmacological quitting aides and novelty items). All participants also received one proactive telephone support call from a peer counsellor. During the study, 85 participants withdrew. The final sample of 216 students who completed baseline questionnaires and 12-week follow-up telephone interviews was representative of the initial sample in terms of demographic characteristics, and smokingquitting- related variables. Results. Whether participants quit smoking depended upon treatment condition, ^(2, N=2\6) = 6.34, p = .04, with Smoke|Quit producing more successfijl quitters (18.4%) than One Step At A Time (4.5%) or the Quit Kit (1 1.4%). On average, participants had quit 53.46 days, with no significant difference across treatments. Selfefficacy also increased. Use of the intervention or other quitting aides was not associated with treatment condition. Among the 191 participants who did not quit smoking, treatment condition did not influence outcomes. Overall, 46.2% had made a quit attempt. Significant decreases in weekly tobacco consumption and increases in self-efficacy to resist smoking were observed from baseline to follow-up. Conclusion. Post-secondary institutions represent a potentially final opportunity for age-targeted interventions. Self-help resources tailored to students' social and contextual characteristics will have considerable more impact than stage-only tailored interventions. Both reduction and abstinence outcomes should be emphasized to positively support students to stop smoking.

Mentorships and co-op placements as a means of heightening the need for a secondary school diploma to the education of at-risk students.--

Both educators and politicians appear to be quite concerned about a dropout rate in Ontario's public schools of some 30 percent. With the basic understanding that a high dropout rate is costly both in economic terms and in human terms, something quite obviously needs to be done to reduce the dropout rate in Ontario schools and, in doing so, ensuring Ontario and its graduates an active role in a growing global economy. This study is an exploratory pilot study in that it examined mentoring and the role that mentoring can play in assisting a student in staying in school and graduating from secondary school. Also incorporated in this is co-operative education and the role it can play, through mentoring, in making students aware of lifestyle level of employment, and of the skills necessary to obtain gainful, meaningful employment. In order to gain information on student attitudes, needs and expectations of a mentoring situation, a series of three questionnaires was used. Also, a questionnaire was distributed to the various co-operative education employers. The intent of this questionnaire was to probe the attitudes, needs and expectations of a mentoring situation from the perspective of an employer. The findings of this study indicated that co-operative education and mentoring are a very valuable and useful component in education. There exist certain factors in a co-operative education setting that serve to enhance and to augment the traditional or "theoretical" setting of the classroom. In addition, a mentoring situation tends to add a sense of relevance to education that students seem to require. Also, an opportunity is offered that allows a student to practice and further refine the skills that have been taught over the course of the student's academic life. Results from this study suggested that a mentoring situation, occurring through a co-operative education situation, adds relevance and a sense of "application" to the traditional or classroom schooling situation. The whole idea of mentoring bodes well for the future of education and of the student. Many advantages are identified in a mentoring situation. One of the advantages is that the schools are able to work quite closely with the community and business in order to stay current and informed on the needs and expected needs of the business community. Co-operative education has now gone beyond being an "experimental" mode of education. All students can benefit from being involved in the program. Certainly at-risk students are aided with staying in school. Those students who are said to be not at-risk can also benefit from being enrolled in the program by gaining hands-on work experience and some of the necessary skills to ensure a place in a growing world economy.

The nature of bullying among secondary school students /

The purpose of this research was to determine the prevalence and effect of bullying in a secondary school. Six hundred and fifty-nine student volunteers completed a survey which included a quantitative component of 40 questions and 3 questions which required a written response. The results suggest that approximately 1 student in 10 was involved in a bullying situation either as a bully or a victim. As age increased, physical bullying decreased whereas psychological remained high in the senior years of high school. Boys were involved more in bullying than girls, especially in the junior years. The effects of bullying could be devastating to the point of school avoidance or early school leaving. The results also indicate that much of the bullying was not being reported. The implication for the education system is that more needs to be done to prevent bullying, to encourage the reporting of bullying, and to deal with the aftermath of a bullying situation.

A qualitative study of authority from the perspective of secondary school principals /

In this research study I examined how four principals of secondary schools interpreted authority and how these interpretations affected their practice. This study involved a presentation of the literature where the concept of qualitative methodology as well as general concepts of authority were reviewed. Four principals were interviewed and asked to reflect on their feelings and experiences as they related to the practice of authority. Five major themes emerged from their reflections and stories which were: Understandings of the Concept of Authority, Principals' Enactment of Authority, Thoughts and Experiences related to Challenges to Their Authority, A View of Principals' Challenge of Authority, and Changing Views on the Authority of Principals in Ontario. The stories of these four principals demonstrated that the practice of authority is complex, dynamic, and contains personal and social tensions. The sharing of these ideas and stories provided a window into the world of these secondary school educational leaders and their experiences with, and enactment of, authority. From this research four recommendations were made to improve educators' practice related to the issue of authority. The importance of this study is that it presents an understanding of the dynamic nature of the process and enactment of authority by these secondary school principals at a unique time in the history of education in Ontario.This qualitative research provides a snapshot of a particular group of educators at a particular time and place. Others need to add to these understandings and modify these ideas through further research. Understanding the experiences of educational leaders as they negotiate concepts of authority gives a window on this very complex, yet vital, component of education.

Bridging the gap between post-secondary students with disabilities and faculty members with their perceptions of access and accommodation

The purpose of this study was to identify factors related to successful university course completion for students with disAbilities including the knowledge that faculty members and students with disAbilities have about accommodation issues; the accommodations that students with disAbilities and faculty use and find effective in the university setting; faculty members' perceptions of and attitudes toward students with disAbilities; and the attitudes that students with disAbilities have toward faculty. Fiftyseven participants were involved in the research, eight students with disabilities and forty-nine faculty members. The main objective of the research was to describe how the skills, knowledge, and attitudes of students and faculty members, and organizational supports interact to support students' academic success. The utilization and effectiveness of accommodations to overcome barriers associated with disAbility in a post-secondary setting are described in relation to students' and faculty members' perceptions of academic success.

Quality time: exploring meaningful mandatory community involvement programs in secondary schools /

The purpose of this study was to explore the experiences of 5 stakeholder groups—students, parents, community organization representatives, guidance counsellors, and secondary school principals—in dealing with a mandatory secondary school graduation requirement in Ontario. The requirement is that students must complete 40 hours of eligible community involvement activities during their high school years in order to graduate. Ten stakeholders were interviewed regarding the nature of the community involvement program, what makes it work, and suggestions for improvement. The study found that although this program has the potential to provide a meaningful experience for students, and students are seen to gain from their experience in multiple ways, it depends substantially on the commitment of students, educators, and community organizations to make it worthwhile. Stakeholders recommended changes to the current program, which included making it a more structured process that would increase the consistency ofhow this program is implemented, finding ways to curb cheating and to reduce the administrative burden on schools, having more support from the Ontario provincial government and Ontario Ministry of Education and Training in the promotion and communication of this program, and developing partnerships between community organizations and schools to enrich the application of this program. This study concludes with a recommendation that the Ontario Ministry of Education and Training consider introducing Service-Learning, a curriculum-based experiential service and learning process, as an enhancement to the current community involvement program.

Transition into the teaching profession: induction and mentoring issues surrounding secondary music teachers /

The purpose of this study was to investigate the issues surrounding the transition into the teaching profession by specifically focusing on teacher induction and mentoring issues while explicitly addressing matters of concern by secondary music teachers in a large suburban school board in southern Ontario. Participants included beginning teachers with fewer than 5 years of teaching, mid career teachers with between 6 and 15 years of instruction, and experienced teachers with more than 16 years of practice. The ' processes of mentoring and inducting new teachers within the board were examined, along with their relationships between proteges, mentors, and administrators. Further, internal and external programs specifically designed and implemented for newer music teachers were scrutinized and discussed. An analysis of key documents and literature on the subject was performed, and data were collected through 16 personal interviews. The findings suggest that although the necessity of mentoring and induction processes has begun to be recognized, there exists a fundamental relationship between mentoring and induction and the effect of the professional attachments to mentoring; the institutional and administrative supports that are enabled; and essential processes and practices between mentors and proteges. Together these three arms combine to support successfiil induction and mentoring initiatives that will help ease the transition into teaching.

"Where is the value in education for me?": experiences and perspectives of Ontario secondary students at risk of non-completion of their Ontario Secondary School Diploma /

This study examined students considered at risk of non-completion of their Ontario Secondary School Diploma and aimed to offer insight into the questions, "What factors currently lead to school disconnect" and "How can these factors be addressed?" Eight students currently enrolled in an alternative learning environment participated in the study. Each was asked to take part in two, digitally recorded interviews that were subsequently transcribed by the researcher. The data were then coded and analysed according to specific themes: obstacles, empowerment, goals, views about success, opinions of school, and power of the teacher. From these themes, three broad focus areas emerged that were used to keep the data analysis focused: worldview, school effects, and self-image. Variances between the data collected and ideas presented in the current literature were highlighted as a reminder that when dealing with a human population, we cannot rely on textbook definitions and theory alone.

Ethical space in a secondary school: a case study /

Discourse in the provincial education system that includes Aboriginal peoples is a convoluted one-sided affair. This has contributed to the limited academic success for Aboriginal secondary students in the provincial school system. The Office of the Auditor General (2004) announced a 27-28 year gap in Academic success compared to non- Aboriginal students (p. I). Both Aboriginal and non-Aboriginal stakeholders are fiiistrated and confused with the lack of support for long-term solutions to address academic success for Aboriginal students. The boundaries in education that exist between the dominant society of Canada and Aboriginal peoples in education are hindering the development of ethical space in which to negotiate and apply "concrete arguments and concepts" (Ermine, 2000, p. 140) for 'best' solutions across the cultural divide. Recent literature suggests a gap in knowledge to address this cultural divide. This study reveals racism is still prevalent and the problem lies in the fallacy of Euro-Western pedagogical beliefs. There is a need to design ethical space that will assist transformation of cross-relations in education for inclusion of Aboriginal voices and content. I submit that ethical space involves physical and abstract space. This report is a qualitative, exploratory, and single case study of one northern Ontario secondary school attended by First Nations and Metis peoples who comprise 35% of the school population. Twenty-six stakeholders volunteered to participate in six interviews. The volunteers in this study are Aboriginal and non-Aboriginal. Aboriginal peoples are firom two First Nations, and Metis peoples. It is an Aboriginal designed and delivered study that a) describes an Aboriginally-designed research method to gather data across cultural divides in a secondary school, b) reviews Tri-Council Policy Section 6 (TCPS) regarding 'good practices' in ethical research involving Aboriginal peoples, and c) summarizes stakeholder perspectives of the 'best educational environment' for one secondary school.

The nature of the highly artistic student in visual arts at secondary school /

This qualitative investigation examined the nature of 7 highly artistic visual arts students at 2 secondary schools in southcentral Ontario. Through interviews, questionnaires, observations, and artwork documents, this study attempted to understand these highly artistic students in terms of creativity, motivation, social and emotional perspectives, and cognitive processes. Data collection occuned over a 3-monlh period. and the data analysis program NVivo 7 was used for coding to develop themes and categories for organizing data. The findings of this study illustrate the significant place that \ isual arts can lake in the growth and development for the youth of today. Participants idcniificd dcxclopnig critical thinking and problem-solving skills, taking risks, and meeting challenges ilirouuh their engagement in the creative process. The transferability of these skills \\ as referenced to numerous aspects of their lives. By enhancing individual perspectives through the study of visual arts, their local and world connections were extended, and environmental and societal concerns evolved. In addition, the communicative opportunities that visual arts provided for these students in terms of personal expression provided emotional health and paths of personal discovery. Through the participants' production of artwork with the many stages this involves, combined with insight into their needs, the participants relayed miportant suggestions for programming enhancements and educational settmgs lor \ isiial arts classrooms. These suggestions are meaningful for educators and curriculum developers of the future.

Synthesis of chiral homoallylic alcohols and phthalans through the asymmetric allylation of carbonyl compounds /

The implementation of chiral centres within biologically active compounds has been a perplexing yet motivational force in chemistry. This work presents the attempted formation of a concurrent or sequential tandem catalyzed methodology of enantioselective nucleophilic addition and electrophilic cyclization. The 2'- arylalkynyl- aldehyde, ketone, and imine substrates used within were adeptly chosen with a dually activated structure; 1) for nucleophilic addition to the electrophilic substituents; and 2) for carbophilic activation of the alkyne substituent to undergo cyclization. To accomplish the nucleophilic addition, two distinct allylation methodologies were pursued: (/?)-BINOL catalyzed-allylboration and (5)- BINAP-AgF catalyzed-allylsilylation. BINAP catalyzed enantioselective allylation of 2'-arylalkynyl-aldehydes, to form chiral homoallylic alcohols, was successful. Homoallylic alcohols were isolated with high enantio-purity (>80%), which then underwent sequential cyclization to form chiral allylic phthalans, in moderate yields. An application of this methodology towards the construction of biologically active compounds was included with the partial synthesis of the natural product and H. pylori inhibitor, (+)-Spirolaxine methyl ether.