Date of Thesis

Fall 2021

Description

There has been interest in studying reactions between organogold compounds and electrophiles due to the relevance of these reactions in gold catalysis. As complexes seen to be both catalysts and intermediates in gold catalytic cycles, arylgold compounds have been part of various discrete studies with electrophiles, such as electrophilic halogen sources and Brønsted acids. Conversely, heteroarylgold compounds have been explored less in these discrete studies with electrophiles, despite also having demonstrated relevance in gold catalysis.

Early synthetic methods used to generate arylgold compounds had a number of limitations, such as long reaction times. Despite advances being made in the development of new synthetic procedures for these products, few syntheses have been published to date on the gram scale. The first portion of this work sought to extend the synthetic method previously developed using (JohnPhos)Au(Br), arylboronic acids and cesium carbonate to generate gram scale amounts of arylgold and heteroarylgold compounds that have never been previously reported. This approach afforded moderate yields of the organogold compounds (72-87%). Characterization of the products was carried out by using NMR spectroscopy, XRD, and qualitative emission under UV irradiation. Finally, a quantitative analysis of the reaction between the arylgold and heteroarylgold compounds, and iodine was carried out in deuterated benzene using 1H NMR spectroscopy. These reactions quickly proceeded to produce JohnPhosAuI and iodoarene products in yields ranging from 85% to 96%. Due to all of the reactions quickly reaching near complete conversion, the reactivity of the different heteroaryl groups could not be distinguished.

Keywords

catalysis, arylgold, synthesis, NMR, XRD

Access Type

Masters Thesis (Bucknell Access Only)

Degree Type

Master of Science

Major

Chemistry

First Advisor

Robert Stockland

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