Date of Completion

7-24-2020

Embargo Period

7-24-2021

Keywords

Photoredox Catalysis, Nitroxides, Visible-Light Energy, Oxidative Transformations, Amides, Nitriles, Carboxylic Acids, Thiazolidine-2-thiones, Phenols

Major Advisor

Nicholas E. Leadbeater

Associate Advisor

Ashis K. Basu

Associate Advisor

Mark W. Peczuh

Associate Advisor

Alfredo Angeles-Boza

Associate Advisor

Anwar B. Beshir

Field of Study

Chemistry

Degree

Doctor of Philosophy

Open Access

Open Access

Abstract

With the growing demand for green and sustainable chemistry, it is imperative to develop novel catalytic methods that involve mild conditions and less toxic reagents. Described herein, is a new paradigm for oxidation and oxidative functionalization methodologies by harvesting visible-light energy. It consists of a dual catalytic system of an environmentally friendly oxidant, 4-acetoamido-2,2,6,6-tetramethylpiperidine N-oxyl (also known as ACT) with photoredox catalysis. The integration of these two forms of catalysis has been realized for the oxidative amidation of aldehydes, furnishing N-acylated heterocycles. Extension of this process to the oxidative amidation of alcohols via the intermediacy of an aldehyde has been successfully pursued in one-pot two-step process, thus offering a general oxidation platform. The applicability of the devised system has been demonstrated for the synthesis of nitriles, amidation of amines, and synthesis of carboxylic acids.

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