Advancements in Visible-Light-Enabled Radical C(sp)²–H Alkylation of (Hetero)arenes

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

The Minisci reaction, which encompasses the radical C–H alkylation of heteroarenes, has undergone revolutionary development in recent years. The application of photoredox catalysis to alkyl radical generation has given rise to a multitude of methods that feature enhanced functional group tolerance, generality, and operational simplicity. The intent of this short review is to bring readers up to date on this rapidly expanding field. Specifically, we will highlight key examples of visible-light-driven Minisci alkylation strategies that represent key advancements in this area of research. The scope and limitations of these transformations will be discussed, with a focus on examining the underlying pathways for alkyl radical generation. Our goal is to make this short review a stepping stone for further synthetic research development. Sections are organized based on alkyl radical precursor reagents.

1 Introduction

2 Alkyl Carboxylic Acids and Carboxylic Acid Derivatives

3 Alkylboronic Acids

4 Potassium Alkyl- and Alkoxymethyltrifluoroborates

5 Alkyl Halides

6 Alcohols and Ethers

7 Conclusion

Key words

Minisci reaction - photoredox catalysis - visible light - radical alkylation - late-stage functionalization - heteroarenes

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