Scope and Limitations of the Palladium-Catalyzed Direct 1,2-Diheteroarylation of 1,2-Dihalobenzene Derivatives

Linhao Liu; Henri Doucet

doi:10.1055/a-1981-3213

Synthesis, Table of Contents

Synthesis 2023; 55(21): 3502-3514
DOI: 10.1055/a-1981-3213

special topic

C–H Bond Functionalization of Heterocycles

Scope and Limitations of the Palladium-Catalyzed Direct 1,2-Diheteroarylation of 1,2-Dihalobenzene Derivatives

Linhao Liu

,

Henri Doucet ∗

Abstract

All articles of this category

Abstract

The reactivity of 1,2-dihalobenzenes in palladium-catalyzed C–H bond functionalization is more difficult to control than that of 1,3- and 1,4-dihalobenzenes because of a possible Pd 1,4-migration during the second catalytic cycle. With C3-substituted heteroarenes this 1,4-palladium migration is not possible and the reaction allows the synthesis of a wide variety of functionalized 1,2-heteroarylated benzene derivatives in high yields. Conversely, only a few heteroarenes with a free C3 position, such as thiazoles, furans and imidazoles, allow the preparation of 1,2-heteroarylated benzenes. Despite these limitations, this one-pot procedure employing an easily available catalyst [Pd(OAc)₂] and an inexpensive base (KOAc) provides a very simple method for the preparation of several 1,2-heteroarylated benzenes.

Key words

C–H functionalization - 1,2-dihalobenzenes - heteroarenes - homogeneous catalysis - palladium

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References

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