Pay roll voucher #35 from the Engineer Department of the Welland Railway for office expenses for the month of October

Pay roll voucher #35 from the Engineer Department of the Welland Railway for office expenses for the month of October. There is an itemized list of staff and jobs on this document, Oct. 31, 1857.

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for repairs of track and sundry work for the month of October

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for repairs of track and sundry work for the month of October, Oct. 31, 1857.

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway on permanent way for sundry work for the month of October

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway on permanent way for sundry work for the month of October.

Pay roll voucher #36 from the Engineer Department of the Welland Railway for the Northern Division for the month of October

Pay roll voucher #36 from the Engineer Department of the Welland Railway for the Northern Division for the month of October, Nov. 3, 1857.

Pay roll voucher #37 from the Engineer Department of the Welland Railway for the Southern Division for the month of October

Pay roll voucher #37 from the Engineer Department of the Welland Railway for the Southern Division for the month of October, Nov. 6, 1857.

Pay roll voucher #38 from the Engineer Department of the Welland Railway for the office for the month of November

Pay roll voucher #38 from the Engineer Department of the Welland Railway for the office for the month of November, Nov. 30, 1857.

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for repairs of track and sundry work for the month of November 30

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for repairs of track and sundry work for the month of November 30, 1857.

Pay roll voucher #43 from the Engineer Department of the Welland Railway for the Northern Division for the month of December

Pay roll voucher #43 from the Engineer Department of the Welland Railway for the Northern Division for the month of December, Dec. 30, 1857.

Pay roll voucher #42 from the Engineer Department of the Welland Railway for the office for the month of December

Pay roll voucher #42 from the Engineer Department of the Welland Railway for the office for the month of December, Dec. 31, 1857.

Pay roll voucher #44 from the Engineer Department of the Welland Railway for the Southern Division for the month of December

Pay roll voucher #44 from the Engineer Department of the Welland Railway for the Southern Division for the month of December, Dec. 31, 1857.

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for repairs of track and sundry work for the month of December

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for repairs of track and sundry work for the month of December, Dec. 1857.

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for locomotive repairs and sundry work for the month of December

Pay roll voucher for foremen, mechanics and laborers of the Welland Railway for locomotive repairs and sundry work for the month of December, Dec. 31, 1857.

Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.

Muster roll (1 page, handwritten) of the Royal Quebec Volunteers of Company no. 3 with Captain W. Power

Muster roll (1 page, handwritten) of the Royal Quebec Volunteers of Company no. 3 with Captain W. Power, Lieutenant J.P. Bradley and Ensign C. Allegn, n.d.