I. Synthesis of enantioenriched 3,4-disubstituted chromans through Lewis base-catalyzed carbosulfenylation II. Development and application of an indium-catalyzed allylation of unprotected carbohydrates

This thesis covers two distinct projects and an additional appendix. The first project is the Lewis base catalyzed carbosulfenylation of unactivated alkenes for the synthesis of chroman scaffolds. The second project is the indium catalyzed allylation of carbohydrates. The final appendix covers the attempted development of a dual catalytic bismuth Lewis acid plus Lewis base system for the activation of epoxides towards nucleophilic capture. Chapters 1 and 2 cover the Lewis base catalyzed synthesis of chroman scaffolds. Chapter 1 begins with an introduction to Lewis base catalysis and the specific Lewis base system that has been employed within the Denmark Laboratories. Prior work on the synthesis of chroman scaffolds is outlined and an initial state of the project, established by Dr. Aragorn Laverny, is detailed. Chapter 2 provides an account of further development of the method, the scope of the method, and efforts to functionalize the chroman products that are formed in the reaction. Chapters 3-5 cover the indium catalyzed allylation of unprotected carbohydrates. Chapter 3 details the development of a catalytic method which can be applied to unprotected carbohydrates under aqueous conditions. A full scope of the reaction is elaborated under multiple different reaction conditions. Chapter 4 provides an overview of mechanistic investigations into the indium catalyzed system. Rigorous NMR studies provide evidence towards several key facets of the reaction and a tentative catalytic cycle is proposed. Finally, Chapter 5 details the attempts to further elaborate the method. Elaborations discussed include iteration of the method for the synthesis of rare sugar scaffolds, utilizing chiral ligands to control the stereochemical outcome of the reaction, and utilizing substituted allylating agents to introduce new functionality. Appendix A covers the attempted development of a bismuth Lewis acid catalytic system which can be activated by Lewis base catalysis. This section covers the impetus for development of the method as well as a brief literature survey of preliminary results related to the proposal. Initial development efforts are discussed as a case study of a small group of ligands tested which are representative of the overall results of our efforts. A full account of the most relevant experiments is further elaborated in the experimental section for this appendix (Chapter 8).

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

2024

Author dc:creator

• Menard, Travis

Contributors dc:contributor

• Denmark, Scott E
• Burke, Martin D
• Sarlah, David
• Mehta, Angad P

• Organic Chemistry
• Organic Synthesis

Statement dc:rights

• Copyright 2024 Travis Menard

Language dc:language

en, eng

Handle dc:identifier

https://hdl.handle.net/2142/125658

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F125658