Synthesis 2020; 52(04): 489-503
DOI: 10.1055/s-0039-1690703
short review
© Georg Thieme Verlag Stuttgart · New York

Pyrylium Salts: Selective Reagents for the Activation of Primary Amino Groups in Organic Synthesis

Yue Pang
a  Department of Organometallic Chemistry, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany   Email: cornella@kofo.mpg.de
,
Daniel Moser
a  Department of Organometallic Chemistry, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany   Email: cornella@kofo.mpg.de
b  Current address: University of Basel, Department of Chemistry, St. Johanns-Ring 19, 4056, Basel, Switzerland
,
a  Department of Organometallic Chemistry, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany   Email: cornella@kofo.mpg.de
› Author Affiliations
We would like to thank the Max-Planck-Gesellschaft, Max-Planck-Institute für Kohlenforschung, Fonds der Chemischen Industrie (VCI) and the CSC scholarship (Y. P.).
Further Information

Publication History

Received: 26 August 2019

Accepted after revision: 11 October 2019

Publication Date:
11 October 2019 (online)


Published as part of the Bürgenstock Special Section 2019 Future Stars in Organic Chemistry

Abstract

Primary amino groups represent an ubiquitous category of functionalities in synthetic building blocks, drugs, and natural products. Therefore, such functionalities offer themselves as perfect handles for late-stage functionalization, and the development of robust and efficient strategies to transform these groups is highly desirable. Despite the extremely challenging activation of the C–N bond, the past few years have witnessed the rapid development of deaminative transformations using pyrylium salts as activating reagents. In most cases, the pyridinium salts formed were activated by single electron transfer, giving alkyl radicals which were used in a series of transformations via nickel and photoredox catalysis. This short review aims to give an overview to related properties of pyrylium salts, their historical significance, and summarize the recent progress in the field of deaminative transformations using these reagents.

1 Introduction

2 Pyrylium and Pyridinium Salts

2.1 Historical Context

2.2 Structure and Reactivity

2.3 Pyrylium Synthesis

2.4 Historical Context of the Reactivity of Pyridinium Salts

3 Recent Progress on Deaminative Transformations of Primary Amino Groups by Pyrylium Salts

3.1 Metal-Catalyzed Cross-Couplings

3.2 Photoredox Catalysis and Photoinduced Reactions for C–C Bond Constructions

3.3 Borylations

3.4 SNAr Functionalization of Aminoheterocycles

4 Conclusion

 
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