Recent Developments in Transition-Metal-Free Functionalization and Derivatization Reactions of Pyridines

Fei-Yu Zhou; Lei Jiao

doi:10.1055/s-0040-1706552

Synlett, Table of Contents

Synlett 2021; 32(02): 159-178
DOI: 10.1055/s-0040-1706552

cluster

Modern Heterocycle Synthesis and Functionalization

Recent Developments in Transition-Metal-Free Functionalization and Derivatization Reactions of Pyridines

Fei-Yu Zhou

,

Lei Jiao∗

Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China Email: leijiao@mail.tsinghua.edu.cn

› Author Affiliations

Abstract

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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

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References

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