Enantiodivergent chemoenzymatic synthesis of codeine

The present thesis describes our latest results in the chemistry of morphine alkaloids. An enantiodivergent synthesis of codeine utilizing a cis-cyclohexadiene diol derived from microbial whole cell oxidation of ~-bromoethylbenzene,as starting material is discussed. The total synthesis of (+)-codeine in 14 steps featuring a Mitsunobu inversion and two intramolecular Heck cyclizations is presented. Investigation of a regioselective nucleophilic opening of a homochiral vinyl oxirane, which led to a total synthesis of the natural isomer of codeine, is detailed. Furthermore, described herein are novel methodologies designed for the transformation of naturally occurring opiates into medicinally relevant derivatives. Two studies on the conversion of thebaine into the commercially available analgesic hydrocodone, two novel ·transition metal catalyzed N-demethylation procedures for opioids, and the development of a catalytic protocol for N-demethylation and Nacylation of morphine and tropane alkaloids are presented. In addition, reactions of a menthol-based version of the Burgess reagent with epoxides are discussed. The synthetic utility of this novel chiral derivative of the Burgess reagent was demonstrated by an enantiodivergent formal total synthesis of balanol. ii

Community Care Access Centre accountability reforms: executive director perceptions /

The purpose of this study was to explore how four purposefully selected executive directors of Community Care Access Centres (CCACs) understood the idea of accountability, and how they viewed the accountability reforms that had been imposed on their sector of health care over the previous three years. Data were collected through personal interviews and a reflective journal. An analysis of key documents and the reflective journal informed the data analysis. The findings suggest that executive directors perceive that accountability relationships have shifted since reforms have been implemented. They noted that CCACs have become more accountable to the provincial government at the expense of accountability to the local community. From their perspective, the demand for greater standardization and bureaucratization has left fewer opportunities to adapt programs to meet particular community needs and has slowed the ability to respond quickly to community inquiries and concerns.

Annual Variation in Bee Community Structure in the Context of Disturbance (Niagara Region, South-Western Ontario)

This study examined annual variation in phenology, abundance and diversity of a bee community during 2003, 2004, 2006, and 2008 in recovered landscapes at the southern end of St. Catharines, Ontario, Canada. Overall, 8139 individuals were collected from 26 genera and sub-genera and at least 57 species. These individuals belonged to the 5 families found in eastern North America (Andrenidae, Apidae, Colletidae, Halictidae and Megachilidae). The bee community was characterized by three distinct periods of flight activity over the four years studied (early spring, late spring/early summer, and late summer). The number of bees collected in spring was significantly higher than those collected in summer. In 2003 and 2006 abundance was higher, seasons started earlier and lasted longer than in 2004 and 2008, as a result of annual rainfall fluctuations. Differences in abundance for low and high disturbance sites decreased with years. Annual trends of generic richness resembled those detected for species. Likewise, similarity in genus and species composition decreased with time. Abundant and common taxa (13 genera and 18 species) were more persistent than rarer taxa being largely responsible for the annual fluctuations of the overall community. Numerous species were sporadic or newly introduced. The invasive species Anthidium oblongatum was first recorded in Niagara in 2006 and 2008. Previously detected seasonal variation patterns were confirmed. Furthermore, this study contributed to improve our knowledge of temporal dynamics of bee communities. Understanding temporal variation in bee communities is relevant to assessing impacts caused on their habitats by diverse disturbances.