Palladium catalyzed cross-coupling of esters and amides
Name
1221004460-MIT.pdf
Size
11.34 MB
Format
Adobe PDF
Checksum (MD5)
d6fde1120b355d55fc2f066655f8215f
Author(s)
Shinabery, Ryan Spence.
Advisor(s)
Stephen L. Buchwald.
Date Issued
2019
Publisher
Massachusetts Institute of Technology
Abstract
Over the last 40 years, great strides have been made in the use of palladium as both a catalyst and a reagent for a multitude of chemical transformations that have had tremendous impacts all walks of life from material science to the development and large-scale synthesis of new, novel pharmaceuticals. One such class of reactions is the palladium-catalyzed functionalization of the [alpha]-position of carbonyl compounds using aryl halides. When compared to palladium catalyzed C-N bond forming reactions, these reactions have been understudied and underutilized. Herein we report our efforts towards the development of the [alpha]-arylation of ethyl acetate by using a continuous flow reactor and a unique lithium amide base. Lessons learned from these studies lead to the development of a simple, one-pot protocol for the mono-[alpha]-arylation of amides under palladium catalysis. Previously reported palladium catalyzed [alpha]-arylations of amides with aryl halides required relatively high catalyst loadings, the use of a glove box, excess ligand, pyrophoric reagents, high temperatures or extended reaction times. This protocol affords the desired mono-[alpha]-arylated amide products in good to excellent yields using 1-2 mol % catalyst loading at ambient temperature in as little as two hours.
Description
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2019
Cataloged from the PDF of thesis. "The Table of Contents does not accurately represent the page numbering"--Disclaimer page.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
MIT theses may be protected by copyright. Please reuse MIT thesis content according to the MIT Libraries Permissions Policy, which is available through the URL provided.
Persistent DSpace Link
