Canada Steamship Lines Limited Richelieu and Ontario Division Niagara to the Sea July 1916

Sailing schedule and trip guide for Canada Steamship Lines Limited for July 1916.

A DFT Guided/Experimental Approach to Asymmetric Allylation and Phase-Transfer Catalysis

The Dudding group is interested in the application of Density Functional Theory (DFT) in developing asymmetric methodologies, and thus the focus of this dissertation will be on the integration of these approaches. Several interrelated subsets of computer aided design and implementation in catalysis have been addressed during the course of these studies. The first of the aims rested upon the advancement of methodologies for the synthesis of biological active C(1)-chiral 3-methylene-indan-1-ols, which in practice lead to the use of a sequential asymmetric Yamamoto-Sakurai-Hosomi allylation/Mizoroki Heck reaction sequence. An important aspect of this work was the utilization of ortho-substituted arylaldehyde reagents which are known to be a problematic class of substrates for existing asymmetric allylation approaches. The second phase of my research program lead to the further development of asymmetric allylation methods using o-arylaldehyde substrates for synthesis of chiral C(3)-substituted phthalides. Apart from the de novo design of these chemistries in silico, which notably utilized water-tolerant, inexpensive, and relatively environmental benign indium metal, this work represented the first computational study of a stereoselective indium-mediated process. Following from these discoveries was the advent of a related, yet catalytic, Ag(I)-catalyzed approach for preparing C(3)-substituted phthalides that from a practical standpoint was complementary in many ways. Not only did this new methodology build upon my earlier work with the integrated (experimental/computational) use of the Ag(I)-catalyzed asymmetric methods in synthesis, it provided fundamental insight arrived at through DFT calculations, regarding the Yamamoto-Sakurai-Hosomi allylation. The development of ligands for unprecedented asymmetric Lewis base catalysis, especially asymmetric allylations using silver and indium metals, followed as a natural extension from these earlier discoveries. To this end, forthcoming as well was the advancement of a family of disubstituted (N-cyclopropenium guanidine/N-imidazoliumyl substituted cyclopropenylimine) nitrogen adducts that has provided fundamental insight into chemical bonding and offered an unprecedented class of phase transfer catalysts (PTC) having far-reaching potential. Salient features of these disubstituted nitrogen species is unprecedented finding of a cyclopropenium based C-H•••πaryl interaction, as well, the presence of a highly dissociated anion projected them to serve as a catalyst promoting fluorination reactions. Attracted by the timely development of these disubstituted nitrogen adducts my last studies as a PhD scholar has addressed the utility of one of the synthesized disubstituted nitrogen adducts as a valuable catalyst for benzylation of the Schiff base N-diphenyl methylene glycine ethyl ester. Additionally, the catalyst was applied for benzylic fluorination, emerging from this exploration was successful fluorination of benzyl bromide and its derivatives in high yields. A notable feature of this protocol is column-free purification of the product and recovery of the catalyst to use in a further reaction sequence.

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.

Memorandum - Report on operations of 1st Division against St. Mihiel Salient, 1918

A memorandum describing the days leading up to the Battle of Saint-Mihiel. The document describes 1. Statement of Operation, 2. Character of Terrain, 3. Initial Dispositions, 4. Suitability of Formations, 5. How such formations were, or could have been, best adapted to meet the changing conditions of combat and terrain, 6. Employment of Infantry Weapons, 7. Artillery Support, 8. Passage of Obstacles, 9. Passage of Lines, 10. Destruction of Opposition, 11. Fighting in Intermediate Zone, 12. Organization of Ground, 13. Liaison, 14. General Observations.

Interrogation of Prisoner - Heaquarters 1st Division, American Expeditionary Forces, 27 May 1918

A prisoner interrogation report dated 27 May 1918. The report reads: "I. PRISONER X. 1st. Battalion, 272 Res. Rogt., 82d Res. 1. CIRCUMSTANCES OF CAPTURE; Captured, while attempting to raid our trenches, at point 1719 at about 7A.M. 2. INFORMATION OBTAINED FROM PRISONER (a) Between point 1814 and point 175242 the German trenches appear to be held by three companies, each numbering 3 platoons, each platoon numbering about 40 men. Each company has 4 light machine guns in the first lines, these machine guns distributed along the first trench (one of them in particular is located at bond in hostile trench at point 17215 and another at about 17245. Each company, furthermore, has one platoon (weak in numbers) in support in the ravine north of Cantigny. These platoons are in dugouts dug into the side of the hill approximately between points 28215 and 2223. Each of these support platoons has two light machine guns at its disposal. Company commanders dugout is at some point along the line of dugouts occupied by the support platoons. Another company commander's dugout (Co.3) is at point 1815 about 15 meters behind the German trench which runs along the edge of the town of Cantigny. There is a communication trench between the cemetery at 2018 and the front line at 18179. It is believed that there is a machine gun at point 17245 kept in a dugout dug under the road. The reserve battalion is believed to be at a fairly great distance from the front (near Bouillancourt). The prisoner, on the other hand, states that it may have been moved up."

Map - First Division Sector Coblenz - Bridghead

A large map titled "Map of First Division Sector Coblenz-Bridgehead" dated 8 May 1919. The map is hand drawn.

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.

Pay roll voucher #13 from the Engineer Department of Port Dalhousie and Thorold Railway Extension for the Northern Division for the month of April, 1857 approved by F. Shanly, chief engineer and W.G. Thompson, assistant engineer, April 27, 1857

Pay roll voucher #13 from the Engineer Department of Port Dalhousie and Thorold Railway Extension for the Northern Division for the month of April, 1857 approved by F. Shanly, chief engineer and W.G. Thompson, assistant engineer, April 27, 1857.

Pay roll voucher #14 from the Engineer Department of Port Dalhousie and Thorold Railway Extension for the Southern Division for the month of April, 1857 approved by F. Shanly, chief engineer and Francis A. Doyle, assistant engineer, April 28, 1857

Pay roll voucher #14 from the Engineer Department of Port Dalhousie and Thorold Railway Extension for the Southern Division for the month of April, 1857 approved by F. Shanly, chief engineer and Francis A. Doyle, assistant engineer, April 28, 1857.

Pay roll voucher # 17 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Northern Division for the month of May, 1857, approved by F. Shanly, chief engineer and W.G. Thompson, assistant engineer, May 27, 1857

Pay roll voucher # 17 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Northern Division for the month of May, 1857, approved by F. Shanly, chief engineer and W.G. Thompson, assistant engineer, May 27, 1857.

Pay roll voucher #18 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Southern Division approved by F. Shanly, chief engineer and F.A. Doyle assistant engineer, May 31, 1857

Pay roll voucher #18 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Southern Division approved by F. Shanly, chief engineer and F.A. Doyle assistant engineer, May 31, 1857.

Voucher from the Engineer Department of Port Dalhousie and Thorold Railway Extension for W.G. Thompson for the Northern Division. There are attached notes from the Welland Railway Company to John Mitchell for putting up shelves; to William Waud, staff; and to William Martin to repair the office (copy), June 10, 1857

Voucher from the Engineer Department of Port Dalhousie and Thorold Railway Extension for W.G. Thompson for the Northern Division. There are attached notes from the Welland Railway Company to John Mitchell for putting up shelves; to William Waud, staff; and to William Martin to repair the office (copy), June 10, 1857.

Pay roll voucher #20 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Northern Division approved by F. Shanly, chief engineer and W.G. Thompson, assistant engineer (copy) June 1857

Pay roll voucher #20 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Northern Division approved by F. Shanly, chief engineer and W.G. Thompson, assistant engineer (copy) June 1857.

Pay roll voucher #21 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Southern Division approved by F. Shanly, chief engineer and Francis A. Doyle, assistant engineer (copy) June 29, 1857

Pay roll voucher #21 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Southern Division approved by F. Shanly, chief engineer and Francis A. Doyle, assistant engineer (copy) June 29, 1857.

Pay roll voucher #26 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Southern Division, for the month of July, 1857 approved by F. Shanly, chief engineer and Francis A. Doyle (copy), July 28, 1857

Pay roll voucher #26 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Southern Division, for the month of July, 1857 approved by F. Shanly, chief engineer and Francis A. Doyle (copy), July 28, 1857.