Copper-Catalyzed C-N Bond Formation from Ketoxime O-Carboxylates and Application to Pyridine Synthesis Público

Abstract

Catalytic quantities of copper (I) or copper (II) sources catalyze the N-imination of boronic acids and organostannanes through reaction with oxime O-carboxylates under non-basic conditions. This method tolerates various functional groups and takes place efficiently using aryl, heteroaryl, and alkenyl boronic acids and stannanes. A simple, modular synthesis of highly substituted pyridines has been achieved by employing a cascade of cross-coupling, electrocyclization, and oxidation reaction starting with α, β-unsaturated ketoxime O-pentafluorobenzoates and alkenylboronic acids with catalytic copper. Readily available starting materials, functionality tolerance, and diverse substitution patterns in the pyridine ring contribute to the power of this method. A strategy utilizing N-N bond disconnection and reconnection for indole synthesis through a decarboxylation and Fischer indole-like cyclization sequence was proved effective. Further study is required to improve the efficiency of the reaction.

Table of Contents

Chapter 1 Copper-Catalyzed N-Imination of Boronic Acids and Organostannanes with O-Acyl Ketoximes 1.1 Introduction and Background 1.2 Results and Discussion 1.2.1 Preparation of Oxime O-Carboxylates 1.2.2 N-Imination of Boronic Acids with Ketoxime O-Carboxylates 1.2.3 N-Imination of Organostannanes with Ketoxime O-Carboxylates 1.2.4 Stereochemistry Study for the Cross-Coupling Reaction 1.2.5 Mechanistic Speculation 1.3 Conclusion 1.4 References 1.5 Experimental Chapter 2 Pyridine Synthesis through a Cross-coupling, Electrocyclization, and Oxidation Cascade Reaction 2.1 Introduction and Background 2.2 Results and Discussion 2.2.1 Preparation of α, β-Unsaturated Ketoxime O-pentafluorobenzoates 2.2.2 Pyridine Synthesis from Alkenylboronic Acids 2.2.3 Pyridine Synthesis from Alkenyl Stannanes 2.2.4 Investigation of Electrocyclization Participation of 3-Azatrienes of Which One Double Bond is part of Aromatic Ring 2.3 Mechanistic Speculation 2.4 Conclusion 2.5 References 2.6 Experimental Chapter 3 Indole Synthesis through a Decarboxylation and Fischer Indole-like Cyclization Sequence 3.1 Introduction and Background 3.2 Results and Discussion 3.3 Conclusion 3.4 References 3.5 Experimental

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School	Laney Graduate School
Department	Chemistry
Degree	PhD
Submission	Dissertation
Language	English
Research Field	Chemistry, Organic
Palavra-chave	imine electrocyclization pyridine copper cascade reaction N-O bond azatriene indole
Committee Chair / Thesis Advisor	Liebeskind, Lanny S, Emory University
Committee Members	Conticello, Vincent, Emory University McDonald, Frank, Emory University

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