Article of agreement between Alexander Cook, contractor of Humberstone and the Provisional Municipal Council of the county of Welland

Article of agreement between Alexander Cook, contractor of Humberstone and the Provisional Municipal Council of the county of Welland to construct and build the main drain through the marsh lands tract commencing in lot no. 27 in the 4th concession in the township of Humberstone in a southerly direction (6 pages, handwritten). This is signed by John Frazer, Provisional Warden, Dexter Deverardo and Alexander Cook. (2 copies), Dec. 30, 1854.

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 clearing and chopping done by Alexander Cook and Andrew Mains

Estimate of clearing and chopping done by Alexander Cook and Andrew Mains, signed by Fred Holmes, Feb. 23, 1855.

Estimate of work done by Alexander Cook, Andrew Mains, Frederick Holmes, Louis Clement, Patrick Roche and Thomas Baird

Estimate of work done by Alexander Cook, Andrew Mains, Frederick Holmes, Louis Clement, Patrick Roche and Thomas Baird, signed by S.D. Woodruff, Feb. 26, 1855.

Estimatesfor clearing done by the contractors including Alexander Cook, Andrew Mains, Frederick Holmes, Louis Clements and Thomas Baird

Estimatesfor clearing done by the contractors including Alexander Cook, Andrew Mains, Frederick Holmes, Louis Clements and Thomas Baird. This document is signed by S.D. Woodruff. This is complete with an envelope made out to S.D. Woodruff, April 28, 1855.

Estimate of work done on marsh lands drainage by Alexander Cook, signed by S.D. Woodruff

Estimate of work done on marsh lands drainage by Alexander Cook, signed by S.D. Woodruff, Nov. 10, 1855.

Estimate of work done on marsh lands drainage by Alexander Cook and Andrew Mains

Estimate of work done on marsh lands drainage by Alexander Cook and Andrew Mains. This is signed by S.D. Woodruff. Also on this sheet is pay roll for engineer services for the months of September, October and November, 1855. This was paid to Frederick Holmes, Thomas Baird, Joseph Simpson and Len [illegible name], Nov.30, 1855.

Estimates for marsh drainage sent to Dexter Deverardo from S.D. Woodruff for Alexander Cook and Andrew Mains

Estimates for marsh drainage sent to Dexter Deverardo from S.D. Woodruff for Alexander Cook and Andrew Mains, Nov. 30, 1855.

Estimate of work done on marsh drainage by Alexander Cook and Andrew Mains

Estimate of work done on marsh drainage by Alexander Cook and Andrew Mains, Nov. 1855.

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook, signed by S.D. Woodruff. Estimate no.7, Jan. and Feb. and Mar., 1856.

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook, signed by S.D. Woodruff. Estimate no.8, April, 1856.

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook, signed by S.D. Woodruff. Estimate no.9, May, 1856.

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook, signed by S.D. Woodruff. Estimate no.10, June, 1856.

County of Welland estimate of work done on constructing a bridge across the tap drain at Marshville by Alexander Lattimer

County of Welland estimate of work done on constructing a bridge across the tap drain at Marshville by Alexander Lattimer, signed by S.D. Woodruff. Estimate no.1, June, 1856.

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook, signed by S.D. Woodruff

County of Welland estimate of work done on the main drain of the marsh lands by Alexander Cook, signed by S.D. Woodruff. Estimate no.11, July, 1856.