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

Liu, Songbai (2007)

Permanent URL: https://etd.library.emory.edu/concern/etds/bn999683c?locale=zh
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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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