Page of scribbled notes and calculations, 1855

Page of scribbled notes and calculations, 1855.

An estimate of work done by Messrs. Brown and McDonell, contractors on sections 1, 2 and 3 ending at St. Catharines for the months of April and May 1855

Scrap of paper that has been burned almost completely. Only the header of the document is intact. It is an estimate of work done by Messrs. Brown and McDonell, contractors on sections 1, 2 and 3 ending at St. Catharines for the months of April and May 1855.

Letter containing a memorandum of the work done during Nov. 1855 by Messrs. Brown and McDonell

Letter containing a memorandum of the work done during Nov. 1855 by Messrs. Brown and McDonell. The work done includes track laying and timber in culverts. There is also a section of the road between St. Catharines and the Great Western Railway where earth has been removed, posts set and laid. This is signed by Francis Lalor, Dec. 12, 1855.

Port Dalhousie and the Thorold Railway pay roll for the months of October, November and December, 1854, signed by S.D. Woodruff, Jan. 8, 1855

Port Dalhousie and the Thorold Railway pay roll for services of engineering and contingencies furnished for the months of October, November and December, 1854, signed by S.D. Woodruff, Jan. 8, 1855.

Port Dalhousie and the Thorold Railway pay roll for the months of January and February, 1855

Port Dalhousie and the Thorold Railway pay roll for services of engineering and contingencies furnished for the months of January and February, 1855.

Port Dalhousie and the Thorold Railway pay roll for the months of October, January, February and March, 1855, signed by S.D. Woodruff, Mar. 22, 1855

Port Dalhousie and the Thorold Railway pay roll for services of engineering and contingencies furnished for the months of October, January, February and March, 1855, signed by S.D. Woodruff, Mar. 22, 1855.

Port Dalhousie and the Thorold Railway pay roll for the months of April and May, 1855, signed by S.D. Woodruff, June 13, 1855

Port Dalhousie and the Thorold Railway pay roll for services of engineering and contingencies furnished for the months of April and May, 1855, signed by S.D. Woodruff, June 13, 1855.

Port Dalhousie and the Thorold Railway pay roll for the months of June, July and August, 1855, signed by S.D. Woodruff. There is an envelope included with this document, Aug. 21, 1855

Port Dalhousie and the Thorold Railway pay roll for services of engineering and contingencies furnished for the months of June, July and August, 1855, signed by S.D. Woodruff. There is an envelope included with this document, Aug. 21, 1855.

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

Note showing the return of time for the preliminary survey of the Port Robinson and Thorold macadamized road for March and April, 1855

Note showing the return of time for the preliminary survey of the Port Robinson and Thorold macadamized road for March and April, 1855.

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.

Time on marsh lands for the months of January, February, March and April for Fred Holmes, Joseph Simpson, Duncan Davidson, Rose Osborne, Henry Wilson and William Baird

Time on marsh lands for the months of January, February, March and April for Fred Holmes, Joseph Simpson, Duncan Davidson, Rose Osborne, Henry Wilson and William Baird. This is signed by Fred Holmes, April 28, 1857.

Abstract of estimates given to Andrew Mains for ditching on the main drain of marsh lands for 1855 and 1856

Abstract of estimates given to Andrew Mains for ditching on the main drain of marsh lands for 1855 and 1856. This is signed by S.D. Woodruff, May 1, 1857.

Engineer services in the marsh lands drainage for the months of December, 1855 and January, February and March of 1856.

Engineer services in the marsh lands drainage for the months of December, 1855 and January, February and March of 1856. Signed by S.D. Woodruff, March 31, 1856.