rdf-syntax-grammar
mods:
  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Selectivity in the amination of allylic alcohols via intramolecular amidomercuration
  name:
    name part: Hollingsworth, Donald Ray
    name part: 1959-
    role:
      role term: creator
  name:
    name part: Harding, Kenn E.
    role:
      role term: degree supervisor.
  name:
    name part: Hazen, Edward E.
    role:
      role term: degree committee member.
  name:
    name part: Meyer, Edgar F.
    role:
      role term: degree committee member.
  name:
    name part: Newcomb, Martin E.
    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: 1989
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: xii, 152 leaves : illustrations ; 29 cm
  abstract: Intramolecular amidomercuration reactions of N-acylaminomethyl ether derivatives of α-substituted allylic alcohols were examined. High stereoselectivity was observed when ethers derived from 4-methyl-1-penten-3-ol and 1-phenyl-2-propen-1-ol were cyclized using mercuric acetate as the electrophile. The cyclization of an ether derived from 3-buten-2-ol gave trans- and cis-4,5-dimethyloxazolidines with moderate stereoselectivity (3:1) under identical conditions. Regioselectivity in intramolecular mercuric-ion initiated cyclizations of N-acylaminomethyl ether derivatives of α,γ-disubstituted allylic alcohols were examined. Mixtures of N-acyl-4,5-dialkyloxazolidine products (125) and N-acyl-4,6-dialkyl-1,3-tetrahydrooxazine products (126) were obtained when either carbamate derived from E-3-penten-2-ol (115E) or Z-3-penten-2-ol (115Z) was treated with mercuric trifluoroacetate. The geometry of the disubstituted double bond (E or Z) was found to affect the regioselectivity. When 115E was cyclized, 1,3-tetrahydrooxazine products (trans-126 and cis-126) predominated over the oxazolidine products in a ratio of 2:1. However, in the cyclization of 115Z, oxazolidine products (trans-125 and cis-125) predominated over the 1,3-tetrahydrooxazine products (2:1). Considering stereochemistry, trans-125 was the major oxazolidine stereoisomer when either 115Z or 115E was cyclized and reduced. However, the stereochemistry of the 1,3-tetrahydrooxazine products depended on the reaction conditions. The kinetically controlled product (cis-126:trans-126 ratio of 17:1), obtained by cyclization of 115E with mercuric trifluoroacetate for 15 min, equilibrated to a 1:29 (cis-126:trans-126) ratio after 11 days of reaction. Likewise, the kinetically controlled product (cis-126:trans-126 ratio of 2:1), obtained by the cyclization of 115Z with mercuric trifluoroacetate for 19 min, equilibrated to a 1:20 diastereomeric ratio of 1,3-tetrahydrooxazines (cis-126:trans-126) after 40 hours of reaction. High…
  note: Typescript (photocopy).
  note: Vita.
  note: "Major subject: Chemistry."
  note: Ph. D. Texas A & M University 1989
  note: Includes bibliographical references.
  subject:
    topic: Stereochemistry
  subject:
    topic: Amination
  subject:
    topic: Organic compounds
    topic: Synthesis
  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:
      url: http://proxy.library.tamu.edu/login
  related item:
    location:
      url: http://gateway.proquest.com/openurl
  record info:
    record content source: TXA
    record creation date: 900627
    record change date: 20200904152439.0
    record identifier: in00000901111
    language of cataloging:
      language term: eng