The preparation of palladium carbene intermediates from diphenylketene is proposed. Experiments to trap these intermediates with alkenes have been conducted and optimized, with cyclopropanes being prepared in up to 69% yield. This methodology has shown to be compatible with olefins, ethers, esters, anhydrides and various benzannulated norbornyl derivatives. In addition, an unusual palladium(II) catalyzed cyclopropane isomerization has been observed. Various substrates have undergone this isomerization affording two different olefin products in up to 61% yield. A catalytic cycle for this process is proposed.

N-Hetereocyclic carbenes (NHC) have been intensively investigated since Ukai et al had reported the first NHC-catalyzed coupling of two equivalents of benzaldehyde, to form what is known as the benzoin product. A plethora of reports have since been published on NHC-catalyzed reactions, such as the cross-benzoin, Stetter, redox reactions, and many others. An attractive feature of NHCs is their ability to effect the umpolung (inversion of reactivity) of aldehydes. The efforts in the introduction of β,γ-unsaturated-α-ketoesters as acceptors for the Stetter reaction have led to the first highly enantioselective intermolecular Stetter reaction with β-aryl substituted Stetter acceptors (up to >99% ee). The synthetic applications of the Stetter adducts generated from the α-ketoester acceptors were demonstrated to give access to a diverse number of useful building blocks. Furthermore, the α-ketoester substrates were found to also be applicable for the cross-benzoin reaction. Through the development of a new electron-deficient, morpholine-based triazolium-derived carbene, a highly chemo- and enantioselective cross-benzoin reaction was achieved using aliphatic aldehydes and α-ketoesters. This methodology constitutes as the first highly enantioselective intermolecular cross-benzoin reaction with aliphatic aldehydes (up to 93% ee). In addition, a highly divergent synthesis of Stetter adducts and cross-benzoin products could be achieved in excellent regioselectivity. Interested in utilizing NHCs as organocatalysts for the development of new reactions, tetrahydrofuran and prolinal derivatives were found to undergo efficient ring-expansions. This methodology gives access to highly functionalized lactones and lactams, which could serve as synthetically useful building blocks for the synthesis of natural products and biologically active compounds.

The preparation of palladium carbene intermediates from diphenylketene is proposed. Experiments to trap these intermediates with alkenes have been conducted and optimized, with cyclopropanes being prepared in up to 69% yield. This methodology has shown to be compatible with olefins, ethers, esters, anhydrides and various benzannulated norbornyl derivatives. In addition, an unusual palladium(II) catalyzed cyclopropane isomerization has been observed. Various substrates have undergone this isomerization affording two different olefin products in up to 61% yield. A catalytic cycle for this process is proposed.

Thesis (M. Sc. (Chemistry))--University of Pretoria, 2001. / Summaries in Afrikaans and English. Also available online.

Thesis (Ph. D.)--University of California, Riverside, 2009. / Includes abstract. Title from first page of PDF file (viewed Mar. 8, 2010). Includes bibliographical references. Issued in print and online. Available via ProQuest Digital Dissertations.

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Thesis (Ph.D.) -- McMaster University, 1997. / In title delta is the Greek letter with superscript 3. Includes bibliographical references. Also available via World Wide Web.

Thesis (Ph.D.) -- McMaster University, 1996. / Includes bibliographical references (leaves [128]-135). Also available via World Wide Web.

Thesis (Ph. D.)--Michigan State University. Dept. of Chemistry, 2006. / Title from PDF t.p. (viewed on June 19, 2009) Includes bibliographical references (p. 229-249). Also issued in print.