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  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Stereoselective synthesis of hydroxypiperidine alkaloids via intramolecular amidomercuration
  name:
    name part: Jones, Michael Wayne
    name part: 1958-
    role:
      role term: creator
  name:
    name part: Harding, Kenn E.
    role:
      role term: degree supervisor.
  name:
    name part: Hogg, John
    role:
      role term: degree committee member.
  name:
    name part: O'Brien, Daniel
    role:
      role term: degree committee member.
  name:
    name part: Wild, James
    role:
      role term: degree committee member.
  name:
    name part: Texas A & M University
    role:
      role term: degree granting institution.
  type of resource: text
  genre: bibliography
  genre: Academic theses
  origin info:
    place:
      place term: xx
    date issued: 1988
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: x, 106 leaves : illustrations ; 29 cm
  abstract: The stereoselective mercuric-ion-initiated cyclofunctionalization of an acylaminomethyl ether derivative of an allylic alcohol was used as a key step in the synthesis of hydroxypiperidine alkaloid derivatives. trans-N-(Cyclohexyloxycarbonyl)-5-(3-benzyloxypropyl)-4-methyloxazolidine was isolated in 65% yield from the cyclization reaction. The benzyl ether was cleaved, and the resulting alcohol was oxidized to the aldehyde, which was treated with dodecyl lithium and oxidized to the ketone. This intermediate served as the common precursor to two isomeric 2,6-dialkyl-3-hydroxypiperidines. Treatment of trans-N-(cyclohexyloxycarbonyl)-4-methyl-5-(3-oxopentadecyl)oxazolidine with hydrogen bromide in nitromethane for 10 minutes at room temperature resulted in an unexpected rearrangement to a cis-N-(hydroxymethyl)oxazolidinone derivative. This material was oxidized to the N-formyl derivative, then treated with base to yield a cyclic imine. Hydrogenation of the imine over palladium on carbon gave racemic 3-isodeoxocassine (6α-dodecy-3β-hydroxy-2α-methylpiperidine). To remove the cyclohexyloxycarbonyl group from the nitrogen and leave the trans oxazolidine intact required heating the oxazolidine at 120°C, with the ketone protected as a cyclic acetal, in 2 M sodium methoxide in methanol in a sealed ampoule for 12 hours. The oxazolidine was opened to the threo aminoalcohol by treatment with pyridine and malonic acid in refluxing ethanol. The acetal was removed and the aminoalcohol was cyclized to the imine by treatment with dilute sulfuric acid in aqueous tetrahydrofuran. Hydrogenation of the imine over palladium on carbon in ethanol gave racemic deoxocassine (6α-dodecy-3β-hydroxy-2α-methylpiperidine). This methodology allowed the stereoselective synthesis of the two isomeric hydroxypiperidines, deoxocassine and 3-isodeoxocassine, from a single precursor. Different carbamate cleavage conditions were used to generate the two different products. In addition to these syntheses, in…
  note: Typescript (photocopy).
  note: Vita.
  note: "Major subject: Chemistry."
  note: Ph. D. Texas A & M University 1988
  note: Includes bibliographical references.
  subject:
    topic: Stereochemistry
  subject:
    topic: Stereoisomers
  subject:
    topic: Molecular structure
  subject:
    topic: Major chemistry
  identifier: http://gateway.proquest.com/openurl
  identifier: http://proxy.library.tamu.edu/login
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    location:
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  record info:
    record content source: TXA
    record creation date: 900131
    record change date: 20200904152422.0
    record identifier: in00000870198
    language of cataloging:
      language term: eng