Palladium-Catalyzed γ-C–H Arylation of Unsaturated Carbonyl Compounds: An Emerging Remote Buchwald–Hartwig–Miura Arylation

Abstract

As an important complement to the Buchwald–Hartwig–Miura arylation, Pd-catalyzed γ-C–H arylations, including γ-C(sp³)–H and γ-C(sp²)–H arylations, provide a more direct route to install an aryl group on the less reactive γ-site of unsaturated carbonyl compounds, and have attracted considerable interest from the chemistry community in recent years. This review summarizes the applications of this method with both cyclic and linear unsaturated carbonyl compounds (aldehydes, ketones, esters, amide, and nitriles), as well as in the total synthesis of natural products (NPs), natural product skeletons, and bioactive analogues.

1 Introduction

2 γ-C–H Arylation of Cyclic Unsaturated Carbonyl Substrates

2.1 Exocyclic γ-Arylation

2.1.1 Unsaturated Ketones and the Corresponding Silyl-Dienol Ethers

2.1.2 Unsaturated Lactones

2.2 Endocyclic γ-C–H Arylation

2.2.1 Unsaturated Ketones and the Corresponding Silyl-Dienol Ethers

2.2.2 Unsaturated Lactones

2.2.3 Unsaturated Nitriles

3 γ-C–H Arylation of Linear Unsaturated Carbonyl Substrates

3.1 Unsaturated Aldehydes

3.2 Unsaturated Ketones

3.3 Unsaturated Amides

3.4 Unsaturated Nitriles

3.5 Silyl Ketene Acetals of α,β-Unsaturated Esters

4 Conclusion