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Title: Proton-Coupled Electron Transfer: Expanding the Substrate Scope of the Aza-Pinacol Coupling Reaction
Authors: Armstrong, Michael
Advisors: Knowles, Robert
Department: Chemistry
Class Year: 2014
Abstract: Multi-site PCET has enabled enantioselective reductive coupling of ketones and hydrazones to form cyclic vicinal amino alcohols. While prior work in the field has demonstrated successful aza-pinacol coupling of aryl ketones, this study aimed to expand the substrate scope to include alkyl ketones and to study the oxidative quenching of the excited Ir\(^{III}\)(ppy)\(_{3}\)* photocatalyst. Out of the five substrates tested, only one demonstrated cyclization. The results of this study suggested that the mechanism of PCET-driven azapinacol coupling proceeds through a ketyl intermediate and that Ir\(^{III}\)(ppy)\(_{3}\)* quenching requires the use of strong irreversible reducing agents. Future work includes further investigation into the mechanism and screening for Ir\(^{III}\)(ppy)\(_{3}\)* quenching. Approaching these challenges experimentally will help to expand the substrate scope and lead to broader applications of PCET in catalytic organic synthesis.
Extent: 91 pages
Type of Material: Princeton University Senior Theses
Language: en_US
Appears in Collections:Chemistry, 1926-2016

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