Persistent Link:
http://hdl.handle.net/10150/290368
Title:
The synthesis of highly substituted indoles via isonitriles
Author:
Kennedy, Abigail Rose
Issue Date:
2001
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
A highly efficient approach to 2,3-disubstituted indoles has been presented. The indole precursors, isonitriles, were used as powerful geminal radical donors/acceptors. The novel isonitrile-alkyne free radical cascade has been efficiently mediated by tin and sulfur. In the case of sulfur, interesting 2,3-dithioindoles were formed. This new class of compounds has exhibited great promise as versatile indole intermediates. In particular, nucleophilic additions at C-10 of the 2,10-dithioindoles were achieved using carbon, sulfur and amine nucleophiles. The versatility of 2,10-dithioindoles was further demonstrated using rhodium-mediated sulfur ylide chemistry. We achieved an intramolecular sulfur ylide reaction which led to a gramine-type addition product 270. Furthermore, sulfur ylides were formed intermolecularly and rearranged to give highly substituted indoles. In studies aimed at the synthesis of the spirotryprostatins, our 2,10-dithioindoles were used in the synthesis of both a simple C-3 spiro-oxindole compound 249 and a diketopiperazine-containing indole derivative 256. This demonstrated the exciting potential of our indole-forming reaction and elaboration methodologies in natural product synthesis.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Chemistry, Organic.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
Rainier, Jon D.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleThe synthesis of highly substituted indoles via isonitrilesen_US
dc.creatorKennedy, Abigail Roseen_US
dc.contributor.authorKennedy, Abigail Roseen_US
dc.date.issued2001en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractA highly efficient approach to 2,3-disubstituted indoles has been presented. The indole precursors, isonitriles, were used as powerful geminal radical donors/acceptors. The novel isonitrile-alkyne free radical cascade has been efficiently mediated by tin and sulfur. In the case of sulfur, interesting 2,3-dithioindoles were formed. This new class of compounds has exhibited great promise as versatile indole intermediates. In particular, nucleophilic additions at C-10 of the 2,10-dithioindoles were achieved using carbon, sulfur and amine nucleophiles. The versatility of 2,10-dithioindoles was further demonstrated using rhodium-mediated sulfur ylide chemistry. We achieved an intramolecular sulfur ylide reaction which led to a gramine-type addition product 270. Furthermore, sulfur ylides were formed intermolecularly and rearranged to give highly substituted indoles. In studies aimed at the synthesis of the spirotryprostatins, our 2,10-dithioindoles were used in the synthesis of both a simple C-3 spiro-oxindole compound 249 and a diketopiperazine-containing indole derivative 256. This demonstrated the exciting potential of our indole-forming reaction and elaboration methodologies in natural product synthesis.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectChemistry, Organic.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorRainier, Jon D.en_US
dc.identifier.proquest3023479en_US
dc.identifier.bibrecord.b41957349en_US
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