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The ultimate goal of organic chemistry is understanding the processes involved in carbon-carbon bond formation. Metalated nitriles are perfectly suited for the regio- and stereospecific creation of sterically congested quaternary centers. These traits are dependent on the metal and the metal's preference for coordination to either the nitrile nitrogen lone pair of electrons or the electron pair of the "anionic" carbon bearing the nitrile. This thesis outlines the structural differences in solution between lithiated, cuprated, and magnesiated nitriles, providing the first such study of magnesiated nitriles. Nuclear magnetic resonance, which has become a powerful tool for a wide variety of structural elucidation, indicates both C- and N- binding modes for magnesium with a high dependence on other functionality present within the nitrile substrate. Carbon-carbon bond formation by the attack of a magnesiated nitrile on an alkene is highly unusual. An intramolecular carbo-magnesiation was serendipitously discovered that involves attack on a terminal alkene followed by addition to the nitrile to give a cyclobutanone. Microwave heating greatly enhances the carbometalation process although the carbometalation has only been achieved in two closely related substrates. Insight into the mechanism was obtained although the reaction scope has not yet been extended to other substrates. / Bayer School of Natural and Environmental Sciences; / Chemistry and Biochemistry / MS; / Thesis;

Reproduction de : Thèse de doctorat : Génie des procédés et de l'environnement : Toulouse, INPT : 2004. / Titre provenant de l'écran-titre. Bibliogr. 92 réf.

Thesis (Ph.D.)--Brown University, 2008. / Vita. Advisor : William C. Trenkle. Includes bibliographical references.

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Thesis (M.S.)--Rochester Institute of Technology, 1991. / Typescript. Includes bibliographical references (leaves 72-74).

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Call number: LD2668 .T4 1962 B66

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The Knoevenagel reaction is defined by the condensation of an aldehyde or ketone with a carbon nucleophile produced by the deprotonation of a methylene species whose acidity is dramatically increased by bonds to strongly electron withdrawing groups. Previously, our group developed an effective one-pot method for the preparation of 4H-chromenes using sodium borohydride reduction of the cyclized intermediates formed by the Knoevenagel condensation of malononitrile with salicylaldehydes in aqueous ethanol. In this study we outline the extension of these strategies to include 2’-hydoxyphenylketones as the starting material. Many of these compounds are also unique and were prepared by Friedel-Crafts acylation of phenols with acyl chlorides and/or Fries Rearrangement of the corresponding phenyl ester. The objective of this project has been to expand the application of the methods optimized in our lab for the simple and efficient formation of carbon-carbon bonds via the selective reduction of the alkylidene portion of the Knoevenagel reaction products. These methods have allowed for the production of several important classes of natural product-like compounds. Specifically, in this investigation, we have adapted these methods to the production of various 4-alkyl and 4-aryl substituted 3-amino-2-cyano-4H-chromenes. These types of molecules exhibit diverse pharmacological activity and have been shown to be potentially useful for the treatment of various diseases. A subset of the synthesized compounds will be submitted to Eli Lilly through their PD2 program. Further variation of substrates included the reaction of salicylaldehydes with ethyl cyanoacetate or cyanoacetamide which provided products unreported in the literature. Reactions with cyanoacetates gave the expected 3-carboethoxy(ester) functionalized 4H-chromene compounds. Products from cyanoacetamide were found to occur in open rather than cyclized forms. / Introduction and background literature -- Synthesis of 2'-hydroxyphenylketones -- Synthesis of 2-amino-3-cyano-4H-chromenes -- One pot method applied to salicylaldehydes with ethylcyanoacetate or cyanoacetamide. / Department of Chemistry