Graduation Year
2024
Document Type
Campus Only Senior Thesis
Degree Name
Bachelor of Arts
Department
Chemistry
Reader 1
Dr. Nicholas D. Ball
Reader 2
Dr. Rebecca C. DiPucchio
Terms of Use & License Information
Rights Information
© 2024 Theo D Yassa
Abstract
Sulfur-Fluoride Exchange (SuFEx) is a powerful synthetic technique capable of accessing important small-molecule sulfur centers relevant to medicinal, agricultural, and materials chemistry. However, the use of traditional transition metal and hydrofluoric-based catalysts to activate the unreactive sulfur (VI) fluoride substrates in these reactions is costly and difficult to implement on a large scale. Lewis acids have been demonstrated as cheap and biocompatible catalysts for other “click”-like reactions, but have yet to be implemented catalytically in SuFEx reactions. This work explores the design and development of a calcium-catalyzed synthesis of sulfonamides via the novel implementation of silylated amine nucleophiles. Because the silyl protecting moiety can coordinate strongly to transition-state fluoride leaving groups, we hypothesized that this will increase catalytic turnover via the prevention of irreversible Ca-F bond forming processes. Through synthetic optimization and quantitative 19FNMR studies, we have concluded that the synthesis of sulfonamides from sulfonyl fluorides and N-silylamines can be catalyzed by the presence of a Lewis acid and a Lewis base under cheap and inoffensive conditions. A variety of structurally diverse and medicinally relevant substrates were tested and their corresponding products were isolated in excellent yield, demonstrating the applicability of this reaction. Future work will explore further optimization of the reaction, particularly in regard to the cost efficiency of Lewis acids, and investigate mechanistic hypotheses via computational and kinetic studies.
Recommended Citation
Yassa, Theo and Ball, Nicholas, "Lewis Acid Catalyzed Sulfur-Fluoride Exchange: A Novel Click Reaction" (2024). Pomona Senior Theses. 305.
https://scholarship.claremont.edu/pomona_theses/305
This thesis is restricted to the Claremont Colleges current faculty, students, and staff.
