The homolytic Brook rearrangement is discussed and homolytic fragmentations of epoxides and epoxysilane chemistry are reviewed. Thiyl radical induced isomerisation was performed on spiro alkenylepoxysilanes to generate novel alkenyl-α-trimethylsilylaldehydes rather than the products of radical Brook rearrangement. The trimethylsilylaldehydes were shown to isomerise on heating to silyldienol ethers and, via the addition of a Grignard reagent, to act as stereoselective vinyl cation equivalents. Attempts to extend the scope of the isomerisation to non-rigid systems met with failure. A review of the antibiotic Roseophilin is presented. Cycloaddition-fragmentation approaches to medium and large rings are reviewed as a prelude to our first route, the proposed Michael addition-retro-aldol fragmentation of the Diels-Alder adduct derived from isopropyl-cyclopentadiene and cyclodec- 2-yn-1-one. The novel ynone, synthesised via the intramolecular Friedel-Crafts acylation of 10-trimethylsilyl-9-decynoyl chloride, was found to isomerise readily to bicyclo[4.4.0]dec-1(6)-en-2-one therefore the model Diels-Alder reaction with cyclopentadiene was effected in one-pot from the cyclisation precursor. Details of the attempted fragmentation of tricyclo[10.2.1.0^2,11]pentadeca-2(11),13-dien-3-one are then described but, due to inconclusive results, an alternative study was instigated. The use of free-radical macrocyclisations in the synthesis of large rings is reviewed with particular reference to the synthesis of natural products. Three strategies for the formation of a bicyclo[10.2.1]pentadecanone skeleton are reported, and subsequent model studies described. Cuprate additions to vinyl lactones and epoxides are discussed. The preferred strategy, involving a cycloalkyl tether between the radical donor and radical acceptor groups, was extended to a system which was derived from the addition of various cuprates to 2-oxabicyclo[3.3.0]oct-7-en-3-one The preparation of cuprates derived directly from 6-iodohexan-1-ol and 1-chloro-6-iodohexane is described. The trans- cuprate addition products were converted successfully to bicyclo[10.2.1]pentadec-12-en-3-one, and the cis- analogues, accessible through a novel regio- and stereoselective hydroboration-fragmentation reaction of 7- (6'-chlorohexyl)-2-oxabicyclo[3.3.0]oct-7-en-3-one, led to bicyclo[10.2.1]pentadec- 13-en-3-one. The successful cyclisations of model oximes, to form nitrones having the correct connectivity for the third ring of Roseophilin, are described. Cuprate additions to 6-(1'-methylethyl)-2-oxabicyclo[3.3.0]oct-7-en-3-one resulted in anti- attack; the cis- adducts were inaccessible via the above methodology but a few intermediates in the trans- series were prepared. Future routes and modifications to the methods developed are then discussed.

While the Boolean satisfiability problem (SAT) lies in NP, prodigious work in SAT solvers has allowed for its use in modeling a multitude of practical problems. Stating a problem in SAT can be cumbersome though and so the demand for SAT encodings arises, providing a means to formulate problems or parts of problems in a more intuitive environment. Several algorithms have been proposed in the past to encode context-free grammars as SAT formulae, allowing for the comprehensive construction of many interesting constraints such as at-most k constraints or such ones pertaining to language syntax. In 2011 a new algorithm was proposed, differing from previous ones in it being based on Earley parsing instead of CYK parsing. Although it performed well for interesting groups of grammars it was later found to behave incorrectly for certain inputs. This thesis discusses the flaws in said algorithm, presents a revision of it and argues for the altered algorithm's correctness. The alterations come with a price, however, and both the running time and output size complexities suffer more-than-quadratic blowup. Since no empirical tests have been performed as of yet, it is still unclear what impact this blowup will have on practical instances.

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While many Internet services and products are free to use, in most cases, they are not completely free. Someone, either the user or a third party, is paying for them either directly or indirectly. By examining the business models of three successful Internet-based companies, this thesis demonstrates the important role that users play in the revenue-generating practices of these companies. Users in these companies are not only customers, but also producers of content for the company. They add value by reviewing products, uploading content, or simply by participating in company-sponsored communities. While many of these activities may be satisfying to users on a personal level, in effect, users are giving up control of the content they produce over to the corporation. The attributes of collaboration and generosity that define truly user-run communities are being exploited by Web 2.0 companies to achieve commercial ends, and as such can only have a semblance of the true spirit of collaboration without all of its substance.

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: Shiping Zhu. Includes bibliographical references.

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: Shiping Zhu. Includes bibliographical references.

Thesis (Ph.D.)--University of Wollongong, 2004. / Typescript. Includes bibliographical references: leaf 333-350.

Thesis (Ph.D.) - Carleton University, 2005. / Includes bibliographical references (p. 399-418). Also available in electronic format on the Internet.

Thesis (M.A. in philosophy)--Washington State University, December 2008. / Title from PDF title page (viewed on Dec. 23, 2008). "Department of Philosophy." Includes bibliographical references (p. 37-39).