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
Menard, Travis
This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.
Permalink
https://hdl.handle.net/2142/125658
Description
Title
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
Author(s)
Menard, Travis
Issue Date
2024-05-31
Director of Research (if dissertation) or Advisor (if thesis)
Denmark, Scott E
Doctoral Committee Chair(s)
Denmark, Scott E
Committee Member(s)
Burke, Martin D
Sarlah, David
Mehta, Angad P
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Organic Chemistry
Organic Synthesis
Abstract
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).
Use this login method if you
don't
have an
@illinois.edu
email address.
(Oops, I do have one)
IDEALS migrated to a new platform on June 23, 2022. If you created
your account prior to this date, you will have to reset your password
using the forgot-password link below.
