Studies directed toward stereoselective synthesis of 1,3-amino alcohols via intramolecular amidomercuration /
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| Other Authors: | , , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
1985.
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| Subjects: | |
| Online Access: | Link to ProQuest copy Link to OAKTrust copy ProQuest, Abstract |
MARC
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| 035 | |a (OCoLC)15511655 | ||
| 035 | |a (OCoLC)ocm15511655 | ||
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| 099 | |a 1985 |a Dissertation |a M351 | ||
| 100 | 1 | |a Marman, Thomas Henry. | |
| 245 | 1 | 0 | |a Studies directed toward stereoselective synthesis of 1,3-amino alcohols via intramolecular amidomercuration / |
| 264 | 1 | |c 1985. | |
| 300 | |a x, 123 leaves : |b illustrations ; |c 29 cm | ||
| 336 | |a text |b txt |2 rdacontent | ||
| 337 | |a unmediated |b n |2 rdamedia | ||
| 338 | |a volume |b nc |2 rdacarrier | ||
| 500 | |a "Major subject: Chemistry." | ||
| 500 | |a Typescript (photocopy). | ||
| 500 | |a Vita. | ||
| 502 | |b Ph. D. |c Texas A & M University |d 1985 | ||
| 504 | |a Includes bibliographical references (leaves 118-122). | ||
| 520 | 3 | |a The cyclization of the benzyl carbamate of 6-hepten-2-amine (31) with mercuric trifluoroacetate in nitromethane over a period of 20 h afforded, after borohydride reduction of the organomercurial, the benzyl carbamate of 2,6-dimethylpiperidine (30a) predominantly (98:2) as the cis diastereomer. Cyclization of 31 with mercuric acetate under similar conditions led to non-stereoselective (60:40 trans:cis) formation of 30a. The kinetically controlled product ratio of 95:5 trans:cis, obtained by cyclization of the benzyl carbamate of 5- hexen-2-amine (37) with mercuric trifluoroacetate for 15 min, was equilibrated, after 9 days of stirring, to a 40:60 trans:cis diastereomeric ratio of the 2,5-dimethylpyrrolidine carbamate. Cyclization precursor 31 was synthesized from 4-bromo-1-butene and ethyl acetoacetate in 5 steps with a 65% overall yield. The benzyl carbamate of 4,6-dimethyltetrahydro-1,3-oxazine (28) was formed by treatment of N-(benzyloxycarbonyl)aminomethyl 4-penten2-yl ether (27) with mercuric trifluoroacetate in a 40% yield or in a 60% yield with anhydrous mercuric nitrate in ethyl acetate after 15 min. A 73:27 cis:trans diastereomeric mixture was obtained. The organomercurial intermediate was equilibrated to a 6:94 cis:trans mixture after 46 h with mercuric nitrate in acetone. Cyclization precursor (27) was formed in two steps from benzyl carbamate in a 51% overall yield. The organomercurial formed from 31 was reduced in the presence of acrylonitrile with sodium borohydride to afford the alkylation product 89 in a 46% yield. Sodium borohydride reduction of the organomercurial from 27 with acrylonitrile led to a 32% yield of alkylation product 91. Reductive alkylation of the mercurial from 27 with - chloroacrylonitrile afforded the corresponding alkylation product (93) in a 16% yield. | |
| 650 | 0 | |a Amino alcohols. | |
| 650 | 0 | |a Stereochemistry. | |
| 650 | 4 | |a Major chemistry. | |
| 655 | 7 | |a Academic theses |2 lcgft | |
| 700 | 1 | |a Baldwin, T. O., |e degree committee member. | |
| 700 | 1 | |a Harding, Kenn E., |e degree supervisor. | |
| 700 | 1 | |a Klein, L. L., |e degree committee member. | |
| 700 | 1 | |a Newcomb, M. E., |e degree committee member. | |
| 710 | 2 | |a Texas A & M University, |e degree granting institution. | |
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