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Synlett 2021; 32(02): 159-178
DOI: 10.1055/s-0040-1706552
DOI: 10.1055/s-0040-1706552
cluster
Modern Heterocycle Synthesis and Functionalization
Recent Developments in Transition-Metal-Free Functionalization and Derivatization Reactions of Pyridines
Financial support from the National Natural Science Foundation of China (Grants Nos. 21772110 and 21822304) is acknowledged.
Abstract
Pyridine is an important structural motif that is prevalent in natural products, drugs, and materials. Methods that functionalize and derivatize pyridines have gained significant attention. Recently, a large number of transition-metal-free reactions have been developed. In this review, we provide a brief summary of recent advances in transition-metal-free functionalization and derivatization reactions of pyridines, categorized according to their reaction modes.
1 Introduction
2 Metalated Pyridines as Nucleophiles
2.1 Deprotonation
2.2 Halogen–Metal exchange
3 Activated Pyridines as Electrophiles
3.1 Asymmetric 2-Allylation by Chiral Phosphite Catalysis
3.2 Activation of Pyridines by a Bifunctional Activating Group
3.3 Alkylation of Pyridines by 1,2-Migration
3.4 Alkylation of Pyridines by [3+2] Addition
3.5 Pyridine Derivatization by Catalytic In Situ Activation Strategies
3.6 Reactions via Heterocyclic Phosphonium Salts
4 Radical Reactions for Pyridine Functionalization
4.1 Pyridine Functionalization through Radical Addition Reactions
4.2 Pyridine Functionalization through Radical–Radical Coupling Reactions
5 Derivatization of Pyridines through the Formation of Meisenheimer-Type Pyridyl Anions
6 Conclusion
Key words
-
pyridine -
functionalization -
derivatization -
transition-metal-free
Publication History
Received: 13 July 2020
Accepted after revision: 30 September 2020
Article published online:
28 October 2020
© 2020. Thieme. All rights reserved
Georg Thieme Verlag KG
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