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Publication Date
2024-5
First Advisor
Alexandra E. Strom
Document Type
Honors Project
Degree Name
Bachelor of Arts
Department
Chemistry
Keywords
competition experiments, mechanistic study, iron catalysis, umpolung chemistry
Abstract
α-Amino carbonyls constitute an important class of pharmaceutically relevant molecular scaffolds due to their potent bioactivity and synthetic versatility as building blocks in organic synthesis. The Strom Lab has demonstrated that these high value synthons can be accessed directly through the iron-catalyzed oxidative coupling of ketones with primary and secondary sulfonamides. However, the reaction mechanism that guides this desirable transformation had previously not been elucidated. The research discussed herein has made progress towards understanding the mechanistic route of catalysis for iron-catalyzed oxidative α-amination by studying the reaction intermediate(s) and the interaction between the iron catalyst and oxidant. It was hypothesized that α-amination is achieved by the in situ formation of an electrophilic center at the ketone α-position, which enables nucleophilic attack of the sulfonamide. This thesis proposes the identity of the α-electrophilic species generated during the reaction mechanism, supported through the synthesis of postulated reactive intermediates and reaction in competition experiments with compatible sulfonamides.
Rights
©2024 Gloria Parrales. Access limited to the Smith College community and other researchers while on campus. Smith College community members also may access from off-campus using a Smith College log-in. Other off-campus researchers may request a copy through Interlibrary Loan for personal use.
Language
English
Recommended Citation
Parrales, Gloria, "Identification of the Reactive Intermediates of the Iron-Catalyzed Oxidative α-Amination of Ketones" (2024). Honors Project, Smith College, Northampton, MA.
https://scholarworks.smith.edu/theses/2631
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Comments
viii, 121 pages: color illustrations, charts. Includes bibliographical references (pages 112-121).