Enantioselective alkene difunctionalization enabled by organochalcogen catalysis I. Lewis base-catalyzed sulfenium ion transfer II. Organoselenium redox catalysis

The thesis herein will cover broadly the application of main group organoselenium catalysis for: (1) the enantioselective transfer of sulfenium ions to alkenes to form lactams, (2) the enantioselective transfer of sulfenium ions to specifically Z-alkenes and the physical organic differences in reactivity between E- and Z-alkenes, and (3) diselenide-catalyzed syn-difunctionalization of alkenes under an oxidative manifold. A further appendix will include work toward the activation and utilization of nitrenium ions for enantioselective aziridination which ultimately was not successful but has important foundational work conducted. Chapter 1 will cover the background of Lewis base catalysis and its application in organic synthesis. Then it will transition into enantioselective sulfenium ion transfer and how the Denmark laboratory has found success with different nucleophiles to afford attractive sulfenofunctionalized products (Chapter 2). These products can be rapidly diversified into a wide variety of useful products under operationally simple transformations. Chapter 3 will expand on the previous discussion by showcasing examples where earlier methodology overlooked critical insights into the catalyst/alkene combination. These studies include both a physical organic look at the mechanism as well as the synthetic applicability. Chapter 4 will change focus to organoselenium redox catalysis whereby a highly electrophilic selenium species becomes susceptible to displacement by careful choice of nucleophile. The selenium species undergoes two displacements to render the whole process catalytic in selenium, a stark contrast to the sulfenofunctionalization discussed in chapters 1-3. The key finding of the addition of fluoride scavengers has the effect of enhancing reactivity in some cases, and in other cases fully ‘turning on’ reactivity. Using a fluoride scavenger has opened up the platform for what is possible under the reaction manifold utilized in these laboratories.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2023

Author dc:creator

• Panger, Jesse Lee

Contributors dc:contributor

• Denmark, Scott E
• Sarlah, David
• Girolami, Gregory S
• Mirica, Liviu M

• Organocatalysis
• Chalcogen
• Enantioselective
• Sulfenofunctionalization
• Lewis Base Catalysis

Statement dc:rights

• Copyright 2023, Jesse Panger

Language dc:language

en, eng

Handle dc:identifier

https://hdl.handle.net/2142/120368

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F120368