A Bicyclic L-Proline Derived Chiral Auxiliary for Asymmetric Synthesis

This thesis describes the use of an L−proline-derived chiral auxiliary for diastereoselective lithiation and ligand synthesis. Such compounds have been utilized in the Metallinos research group previously for the synthesis of N−substituted planar chiral ferrocenes. The first project describes the use of this chiral auxiliary as a directing group for N−benzyl substitution, providing products in up to 10:1 diastereomeric ratio (dr). These derivatives may serve as chiral ylidene precursors to serve as ligands in transition metal catalysis. In addition, an N−substituted planar chiral ferrocene ylidene ligand derived from the same chiral auxiliary was used to prepare rhodium complexes that were explored as potential catalysts for asymmetric hydroformylation.

Asymmetric cyclopropanation via catalysts incorporating the 1,4-diol ligands and the newly designed dioxaborolane /

The development of new methodology for the asymmetric synthesis of chiral organic compounds is a major focus in modem organic chemistry. The use of chiral catalysts is replacing chiral auxiliaries as a new tool for synthetic chemists. An efficient chiral catalyst allows for large quantities of optically active product to be obtained on use of relatively small amount of enantiopure material, without the need for the removal and recovery of a chiral auxiliary. Furthermore, the most practical catalytic methods utilize an inexpensive and readily available chiral ligand that can provide high and predictable enantioselectivity across a wide range of substrates. In our project, two type of versatile, upgraded chiral ligands have been designed and synthesized. Their application in Simmons-Smith type cyclopropanation is investigated, and the pleasing results suggest that they are the potential catalytic enantioselective candidates to build C-C bonds.

Development of thermally stable versions of the Burgess Reagent : approaches to the chemoenzymatic total synthesis of morphine

The present studies describe our recent work on expanding the use of the Burgess reagent and its reaction with oxiranes. Several new variants of the Burgess reagent and its chiral auxiliary version were evaluated for their thermal stability by NMR spectroscopy. Three new versions of the reagent were synthesized and their stability was determined. The reactivity of all five Burgess reagents was compared in a dehydration reaction and reactions with epoxides and diols. Progress toward a chemoenzymatic synthesis of morphine is also included in this report. The synthesis began with the whole cell oxidation of bromobenzene by Escherichia coli JMI09(pDTG601). The preparation of several precursors for a key step involving the lohnson-Claisen rearrangement and progress toward the total synthesis are described.

Anne McPherson family fonds, 1852-2011 [non-inclusive]

Frank C. (Case) McCordick (1873-1946) was the son of William Henry (1849-1930) and Emily D. Howell (1851-1927) McCordick. William H. McCordick was in the coal business. The McCordick family included Frank Case, Mabel Gertrude, Ethel Howell and Arthur Stanley. Frank C. McCordick was educated in St. Catharines, and worked with his father in the coal business and eventually opened up a leather tanning operation. McCordick was active in the Lincoln Regiment and in 1906 was promoted to captain and in command of Company A, 19th Regiment. He was promoted to major and at the outbreak of war he was sent overseas as a commander of the 35th Battalion of the Canadian Expeditionary Forces (CEF). Upon arrival in France he was made officer commanding the 15th Battalion, King’s Own Yorkshire Light Infantry (KOYLI). After the war and his return to Canada he continued to play an active role in the local military units in the area as well as in Hamilton. After his retirement from the military in 1927 McCordick served as alderman and then mayor of St. Catharines from 1930 to 1931. He was a member of a large number of civic clubs, including St. Catharines Chamber of Commerce, Y.M.C.A., Lion’s Club, St. Catharines Golf Club, Detroit Boat Club, the St Catharines Club, as well as a member of several Masonic lodges. He continued to operate McCordick Tannery and other local investments. In 1903 Frank C. McCordick married May Beatrice Simson, daughter of Thomas E. Simson of Thorold. They had three children, E. (Edward) Frank McCordick, Bruce McCordick and (Margaret) Doris McCordick (m. Hubert Grigaut, d. 1977). The McCordick family resided at 82 Yates Street, near Adams Street. May Simson McCordick (b. 1873) was the daughter of Thomas Edward (1836-1908) and Julia Headlam (1844-1887) Simson of Thorold. Her siblings included: Edward, Frances, John, Augusta, Georgia and Gertrude. E. (Edward) Frank McCordick (1904-1980) was born in St. Catharines, Ont., attended Lake Lodge School in Grimsby, Ridley College in St. Catharines, Beechmont Preparatory School in England, Upper Canada College in Toronto and graduated from Royal Military College in Kingston, Ont. in 1925. Upon graduation he was made a lieutenant in the 10th (St. Catharines) Field Battery. In 1929 he married Helen Stanley Smith, daughter of Stanley George and Mary Walker Smith of St. Catharines. Col. McCordick, now promoted to Major, played an active role in the 10th (St. Catharines) Field Battery, being officer commanding the battery. In late 1939 McCordick headed to England for artillery tactical training and on December 6, 1939 the battery began the long trek overseas. McCordick saw action in Italy and in Holland. Upon his return to Canada at the end of the war he was the Liberal candidate in the federal election for Lincoln County. He remained active in the local military serving as honorary lieutenant-colonel of the 56th Field Regiment (ARCA) and in 1976 as the honorary colonel of the regiment. Col. McCordick held the Efficiency Decoration, the Order of the British Empire, granted in 1945 and was made an officer in the Order of St. John in 1978. He continued to serve his community in various capacities, including the Unemployment Insurance Canada Board, Royal Trust Company and the St. John Ambulance Society. He remained an active member of the alumni of Royal Military College, editing and compiling a newsletter and organizing reunion weekends. He kept in close contact with many of his classmates. Helen Stanley Smith McCordick lived in St. Catharines, Ont., attended Robertson School, and graduated from the University of Toronto in 1926 with a Bachelor of Arts degree in Modern Languages. During the war years (1939-1945) Helen was active in the Transport division of the local branch of the Canadian Red Cross and the Women’s Auxiliary of the 10th Field Battery. In 1932 E. Frank and Helen McCordick welcomed their only child, (Catharine) Anne McCordick. Helen continued to play an active role in her community until her passing in 1997. Stanley George Smith (1865-1960) was born in St. Catharines, Ont., the only child of William Smith (d. June 16, 1876) a native of Edinburgh, Scotland and his wife Hannah Louisa Maria Bulkeley a native of Fairfield, Connecticut. Stanley George Smith married Mary Walker of Guelph, Ont.(d. 1956) Mary was the daughter of Hugh and Elizabeth (d. 1924) Walker. Her siblings included Margaret, Agnes, Jessie, Isabella, Lorne, Ada, Alice, Eva, Alexander and George. Hugh Walker was a prominent fruit and vegetable merchant in Guelph. On 1904 their only child, Helen Stanley Smith was born. He was a post office clerk, and the treasurer for the James D. Tait Co. Ltd., a clothing and dry goods retailer in St. Catharines. The family lived at 39 Church Street in St. Catharines, Ont.

Synthesis and utilization of guanidine catalysts for applications directed towards the preparation of butenolide and modified amino acid derivatives

Development of guanidine catalysts is explored through direct iminium chloride and amine coupling, alongside a 2-chloro-l,3-dimethyl-IH-imidazol-:-3-ium chloride (DMC) induced thiourea cyclization. Synthesized achiral catalyst N-(5Hdibenzo[ d,t][1,3]diazepin-6(7H)-ylidene)-3,5-bis(trifluoromethyl) aniline proved unsuccessful towards O-acyl migrations, however successfully catalyzed the vinylogous aldol reaction between dicbloro furanone and benzaldehyde. Incorporating chirality into the guanidine catalyst utilizing a (R)-phenylalaninol auxiliary, generating (R)-2-((5Hdibenzo[ d,t] [1,3 ]diazepin-6(7H)-ylidene ) amino )-3 -phenylpropan-l-ol, demonstrated enantioselectivity for a variety of adducts. Highest enantiomeric excess (ee) was afforded between dibromofuranone and p-chlorobenzaldehyde, affording the syn conformation in 96% ee and the anti in 54% ee, with an overall yield of30%. Attempts to increase asymmetric induction were focused on incorporation of axial chirality to the (R)phenylalaninol catalyst using binaphthyl diamine. Incorporation of (S)-binaphthyl exhibited destructive selectivity, whereas incorporation of (R)-binaphthyl demonstrated no effects on enantioselectivity. Current studies are being directed towards identifying the catalytic properties of asymmetric induction with further studies are being aimed towards increasing enantioselectivity by increasing backbone steric bulk.

Fair of Nations (1906)

Official program "Fair of Nations" for the benefit of the Niagara Falls General Hospital.

Diastereoselective Synthesis of Planar Chiral N-Substituted Ferrocenes Derived from Epimeric Imidazolones and their Application to Asymmetric Hydrogenation of Quinolines

This thesis describes the synthesis and use of an N-substituted ferrocene bearing a proline-derived chiral directing group and diastereoselective lithiation-electrophile quench of the pro-Sp hydrogen of the ferrocene to give planar chiral products in >95:5 dr. The auxiliary group is found to be stable to lithium bases of types RLi and R2NLi giving the same diastereoselectivity. The anti- epimer of the previously mentioned syn auxiliary induces lithiation of pro Rp rather than pro Sp hydrogen in >95:5 dr. Upon electrophile quench and elimination, the enantiomer of the syn-derived planar chiral imidazolone is obtained. Hence, this method provides a practical way to prepare planar chiral enantiomers in this series without the use of a more expensive D-proline derived starting material. The syn and anti epimers have β, γ-stereogenic centers and the origin of stereoselectivity in lithiation appears to be driven by the conformational bias exerted by the β-silyloxy moiety in each chiral auxiliary. In the thesis, this conclusion is supported using insensitivity of lithiation selectivity to the bulkiness of the base, comparison of enantiomers, deuteration experiments, nOe difference studies and computational modeling of the ground states and lithiation transition states for both substrates. The products are then converted to ligand precursors to make iridium and rhodium complexes. Among them, one of the cationic iridium complex is found to be effective in the asymmetric hydrogenation of 2-substituted quinolines with enantioselectivities up to 80% at pressures as low as 5 atm.

Volunteering and Social Capital: A Case Study of Older Hospital Volunteers in Southern Ontario

Volunteering as a form of social activity can facilitate older adults’ active aging through community engagement. The purpose of this qualitative case study was to understand the views on older adults’ volunteerism in a community hospital network in Southern Ontario. Utilizing in-depth interviews with 10 older volunteers (over the age of 65), document analysis, and a key informant interview, I explored their experiences of volunteering and social capital development at six hospitals in the network. Data analyses included open and axial coding, and conceptualization of the themes. Four major themes emerged from the data: reasons to volunteer, management’s influence, negative experiences of volunteering, and connections with others. The findings of this research emphasized older volunteers’ strong commitment and enthusiasm to support the hospital in their own communities, the power of volunteering to enhance the development of bonding, bridging, and linking social capital, and the influence of two major contextual factors (i.e. the Auxiliary Factor and the Change Factor) to facilitate or hinder older volunteers’ social capital development in the hospitals. Future research directions should focus on further unpacking the different degrees to which each type of social capital is developed, placing emphasis on the benefits of social capital development for volunteers in healthcare settings. The implications for practice include the targeted recruitment of older adults as healthcare volunteers while creating volunteer positions and environments in which they can develop social capital with their peer volunteers, hospital staff, patients, and people in surrounding communities. To sustain their existing dedicated long-term volunteers, in particular their Auxiliary groups, the community hospital network can enhance facilitating factors such as the Auxiliary Factor while mitigating the negative effects of the Change Factor. By developing social capital through volunteering in their own communities, older adults can engage in active aging, while participating in the development of an age-friendly community.