2026-09-23T17:54:59Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/344942022-01-13T07:54:21Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Rick L. Danheiser.
Thongsornkleeb, Charnsak
Massachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2006-11-07T12:31:25Z
2006-11-07T12:31:25Z
2006
2006
http://hdl.handle.net/1721.1/34494
70851652
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006.
Vita.
Includes bibliographical references.
Studies directed toward the synthesis of the A-ring portion of glycinoeclepin A are described. The enantioselective synthesis of key diketone intermediate 128 in four steps from 2,2-dimethyl-1,3-cyclohexanedione (5) has been accomplished via the acid-catalyzed intramolecular Michael cyclization of an enone generated in situ from 132. In the course of these studies, a new method for the preparation of the highly reactive a-alkynyl acroleins was developed. Several methods for the further elaborations of diketone 128 to the key enyne intermediate 95 were investigated and the best route developed to date involves the conversion of the methyl ketone to a vinyl triflate (177) followed by Sonogashira coupling. In addition, the conversion of diketone 128 to the vinyl halide 258 via a Shapiro strategy was achieved and model studies were carried out on the synthesis of vinylallene by coupling cuprate derivatives of this intermediate with propargyl alcohol derivatives.
by Charnsak Thongsornkleeb.
Ph.D.
188 p.
6542541 bytes
6550439 bytes
application/pdf
application/pdf
eng
Massachusetts Institute of Technology
M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.
http://dspace.mit.edu/handle/1721.1/7582
Chemistry.
Studies toward the total synthesis of glycinoeclepin A
Thesis
application/pdf
Publication
unknown
unknown
<Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="334578f9-49e0-48b4-aac7-dde86d63c2f7">
<Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type>
<Language>eng</Language>
<Title>Studies toward the total synthesis of glycinoeclepin A</Title>
<PublishedIn>
<Publication>
</Publication>
</PublishedIn>
<PublicationDate>2006</PublicationDate>
<Authors>
<Author>
<DisplayName>Thongsornkleeb, Charnsak</DisplayName>
<Affiliation>
<OrgUnit>
</OrgUnit>
</Affiliation>
</Author>
</Authors>
<Editors>
</Editors>
<Publishers>
<Publisher>
<DisplayName>Massachusetts Institute of Technology</DisplayName>
<OrgUnit />
</Publisher>
</Publishers>
<License>http://dspace.mit.edu/handle/1721.1/7582</License>
<Keyword>Chemistry.</Keyword>
<Abstract>Studies directed toward the synthesis of the A-ring portion of glycinoeclepin A are described. The enantioselective synthesis of key diketone intermediate 128 in four steps from 2,2-dimethyl-1,3-cyclohexanedione (5) has been accomplished via the acid-catalyzed intramolecular Michael cyclization of an enone generated in situ from 132. In the course of these studies, a new method for the preparation of the highly reactive a-alkynyl acroleins was developed. Several methods for the further elaborations of diketone 128 to the key enyne intermediate 95 were investigated and the best route developed to date involves the conversion of the methyl ketone to a vinyl triflate (177) followed by Sonogashira coupling. In addition, the conversion of diketone 128 to the vinyl halide 258 via a Shapiro strategy was achieved and model studies were carried out on the synthesis of vinylallene by coupling cuprate derivatives of this intermediate with propargyl alcohol derivatives.</Abstract>
<Access xmlns="http://purl.org/coar/access_right"
>
</Access>
</Publication>