Pay roll voucher #24 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the office, for the month of July, 1857 approved by F. Shanly, chief engineer (copy), July 31, 1857

Pay roll voucher #24 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the office, for the month of July, 1857 approved by F. Shanly, chief engineer (copy), July 31, 1857.

Voucher from the Engineer Department of Port Dalhousie and Thorold Railway Extension to W.G. Thompson regarding horse hire (copy), Jul. 30, 1857

Voucher from the Engineer Department of Port Dalhousie and Thorold Railway Extension to W.G. Thompson regarding horse hire (copy), Jul. 30, 1857.

Pay roll voucher #25 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Northern Division, for the month of July, 1857 approved by F. Shanly, chief engineer and W. G. Thompson (copy), July 30, 1857

Pay roll voucher #25 from the Engineer Department of Port Dalhousie and Thorold Railway Extension, for the Northern Division, for the month of July, 1857 approved by F. Shanly, chief engineer and W. G. Thompson (copy), July 30, 1857.

Pay roll voucher #27 from the Engineer Department of the Welland Railway for sundries for the month of August, 1857. A section of the list has been cut from the page, Aug. 31, 1857

Pay roll voucher #27 from the Engineer Department of the Welland Railway for sundries for the month of August, 1857. A section of the list has been cut from the page, Aug. 31, 1857.

Pay roll voucher #30 from the Engineer Department of the Welland Railway for the Southern Division for the month of August, Aug. 31, 1857

Pay roll voucher #30 from the Engineer Department of the Welland Railway for the Southern Division for the month of August, Aug. 31, 1857.

Letter to S.D. Woodruff regarding a resolution passed that the engineer be requested to examine the fence built by the contractors alongside of the Henry Vandenburgh Farm

Letter to S.D. Woodruff regarding a resolution passed that the engineer be requested to examine the fence built by the contractors alongside of the Henry Vandenburgh Farm and report to the secretary as to whether this is a lawful fence, completed according to Williams’ contract. This is signed by Duncan McFarland, president. There is a reply written by S.D. Woodruff at the bottom of the letter stating that the fence is not built in accordance with the contract, Dec. 18, 1856.

This document is very badly burned, it includes: a schedule of construction, May 28, 1855 and value of work used for constructing the bridge crossing at Chippawa Creek, Oct. 1857

This document is very badly burned, it includes: a schedule of construction, May 28, 1855 and value of work used for constructing the bridge crossing at Chippawa Creek, Oct. 1857. It is signed by S.D. Woodruff (3 pages, handwritten). Almost all text is illegible, 1857

Letter with the salutation “Dear Sir” It is signed by John I. Mackenzie in which he states that he got the Globe to publish a letter about the Long Point expats which had been sent to the Ottawa Times

Letter with the salutation “Dear Sir” It is signed by John I. Mackenzie in which he states that he got the Globe to publish a letter about the Long Point expats which had been sent to the Ottawa Times. Most of the handwriting is illegible, Oct. 26, 1870.

Letter from John I. Mackenzie with the salutation “Dear Sir”

Letter from John I. Mackenzie with the salutation “Dear Sir” which states that Col. Tisdale and Hunter discussed the desirableness of transferring 5 of your shares over to Mackenzie (2 pages, handwritten). He also says that they will need funds for wages, March 28, 1878.

Letter (printed) with the salutation “Dear Sir”. The writer is John I. Mackenzie.

Letter (printed) with the salutation “Dear Sir”. The writer is John I. Mackenzie who outlines resolutions which were passed at the annual meeting of the Long Point Co., June 21, 1879.

Letter with the salutation “Dear Sir” and signed by Louis Cabot

Letter with the salutation “Dear Sir” and signed by Louis Cabot. He claims that he has written to George Richards to send a draft for $1,000.00 (2 pages, handwritten), March 23, n.d.

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.

Estimate of work done by A. Cook on the marsh lands main drain during the month of June 1857

Estimate of work done by A. Cook on the marsh lands main drain during the month of June 1857. This is signed by Fred Holmes, June 30, 1857.

Time on the marsh lands for the months of May, June, July and August, 1857 for Fred Holmes, Joseph Simpson and William Baird

Time on the marsh lands for the months of May, June, July and August, 1857 for Fred Holmes, Joseph Simpson and William Baird. This was sent to S.D. Woodruff by Fred Holmes, Aug. 28, 1857.

Engineering services in marsh lands drainage for the months of May, June, July and August 1857 for Fred Holmes, Joseph Simpson and William Baird

Engineering services in marsh lands drainage for the months of May, June, July and August 1857 for Fred Holmes, Joseph Simpson and William Baird. This is signed by S.D. Woodruff, Aug. 31, 1857.