2026-09-20T16:00:19Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/843792022-01-13T07:53:58Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Rick L. Danheiser.
Willumstad, Thomas P. (Thomas Paul)
Massachusetts Institute of Technology. Department of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2014-01-23T18:40:10Z
2014-01-23T18:40:10Z
2013
2013
http://hdl.handle.net/1721.1/84379
867637770
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2013.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Benzannulations employing ynamides and vinylketenes (generated in situ from [alpha]-diazo ketones) were investigated. Irradiation of the diazo ketones using a batch or continuous-flow reactor leads to the formation of vinylketenes via a photo-Wolff rearrangement. The vinylketenes then react with ynamides via a pericyclic cascade process to produce highly substituted aniline derivatives. Using this vinylketene-based benzannulation, tandem strategies for the synthesis of highly substituted benzo-fused nitrogen heterocycles were investigated. A tandem benzannulation-iodocyclization method for the synthesis of polysubstituted quinolines was established. In addition, a tandem strategy for the synthesis of carbazoles was developed and applied in the total synthesis of the carbazole alkaloid carazostatin as well as formal syntheses of the alkaloids carbazoquinocin C and antiostatin A₄.
by Thomas P. Willumstad.
Ph.D.
345 pages
eng
Massachusetts Institute of Technology
M.I.T. theses are protected by
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http://dspace.mit.edu/handle/1721.1/7582
Chemistry.
Synthesis of highly substituted benzo-fused nitrogen heterocycles via tandem benzannulation/cyclization strategies
Thesis
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Publication
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<Abstract>Benzannulations employing ynamides and vinylketenes (generated in situ from [alpha]-diazo ketones) were investigated. Irradiation of the diazo ketones using a batch or continuous-flow reactor leads to the formation of vinylketenes via a photo-Wolff rearrangement. The vinylketenes then react with ynamides via a pericyclic cascade process to produce highly substituted aniline derivatives. Using this vinylketene-based benzannulation, tandem strategies for the synthesis of highly substituted benzo-fused nitrogen heterocycles were investigated. A tandem benzannulation-iodocyclization method for the synthesis of polysubstituted quinolines was established. In addition, a tandem strategy for the synthesis of carbazoles was developed and applied in the total synthesis of the carbazole alkaloid carazostatin as well as formal syntheses of the alkaloids carbazoquinocin C and antiostatin A₄.</Abstract>
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