Author ORCID Identifier
Document Type
Thesis
Date of Award
Fall 12-9-2022
Keywords
Hydroetherification, Photoredox
Degree Name
Chemistry (BA, BS)
Department
CHEMISTRY
First Advisor
Dr. Jennifer Hirschi
Second Advisor
Dr. Brian Callahan
Third Advisor
Dr. Rebecca Kissling
Series
Science and Mathematics
Subject Heading(s)
Etherification--Methods; Photochemistry--Research
Abstract
The development of olefin hydroetherification reactions via the addition of an alcohol nucleophile and hydrogen atom across an unsaturated carbon-carbon bond has remained a sought- after synthetic transformation. The formation of ethers via this methodology has traditionally required the use of transition metals and/or harsh conditions to catalyze the reaction and is challenging to make selective. However, the Nicewicz laboratory has since developed an anti- Markovnikov intramolecular hydroetherification of alkenols using photoredox catalysis. With the mechanism of this pivotal transformation—and of photoredox reactions in general—being largely unexplored mechanistically, the Hirschi lab implemented experimental 13C kinetic isotope effects (KIEs) and density functional theory (DFT) to elucidate the mechanism of this transformation. A key finding was the role base additives play in the rate-limiting step of the reaction. Knowledge of the mechanism has enabled mechanism-driven reaction design to improve the rate, efficiency, yield, and capabilities of this reaction.
Recommended Citation
Loyer, Kimberly A., "Photocatalytic Anti-Markovnikov Hydroetherification of Olefins" (2022). Undergraduate Honors Theses. 20.
https://orb.binghamton.edu/undergrad_honors_theses/20