Graduation Year
2024
Document Type
Campus Only Senior Thesis
Degree Name
Bachelor of Arts
Department
Chemistry
Reader 1
Nicholas D. Ball
Reader 2
Matthew H. Sazinsky
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Rights Information
© 2024 Matt Teeter
Abstract
Sulfur(IV)-containing molecules are of great interest to chemists and can be found in a wide array of agrochemicals, pharmaceuticals, and materials.In addition, S(VI) motifs have been shown to be valuable tools in organic synthesis, with S(VI)-fluorides serving as hubs for connecting molecular building blocks in the synthesis of complex products through sulfur-fluorine exchange (SuFEx) reactions. S(VI)-fluorides are attractive starting materials due to the latent reactivity of the S-F bond, which can remain unreacted in the course of a larger synthesis but can be activated for nucleophilic attack under certain conditions, usually by a Lewis acid. Typical SuFEx reactions involve a nitrogen or oxygen nucleophile, forming sulfonamides or sulfonate esters, respectively, but reactions with carbon nucleophiles have not been well-explored. Those which have been elucidated are limited in their applicability due to harsh reaction conditions.
In collaboration with our colleagues at Pfizer, a SuFEx sulfonylation reaction which makes use of a methyl ester enolate nucleophile to form alkyl aryl sulfones is presented. Notably, these conditions are carried out in one pot, and there is preliminary evidence that suggests that a variety of functional groups are tolerated. In addition, the reaction proceeds through an α-ester sulfone intermediate, which is then decarboxylated to yield the sulfone product; this intermediate structural motif is relatively unexplored, and this synthetic route constitutes a novel approach to the synthesis of sulfones. However, yields of this intermediate remain a challenge, and investigating the addition step of the reaction through enolization studies and the role of metal counterions, such as lithium and calcium, in the activation of the S-F bond for nucleophilic attack will help to improve the proposed conditions. In addition, a broad substrate scope will help to demonstrate the applicability of these conditions.
Recommended Citation
Teeter, Matt and Ball, Nicholas, "Development of a Decarboxylative SuFEx Reaction for the Synthesis of Sulfones" (2024). Pomona Senior Theses. 308.
https://scholarship.claremont.edu/pomona_theses/308
This thesis is restricted to the Claremont Colleges current faculty, students, and staff.
