Lewis acid-mediated Suzuki–Miyaura cross-coupling reaction

Abstract

The palladium-catalysed Suzuki–Miyaura cross-coupling reaction of organohalides and organoborons is a reliable method for carbon–carbon bond formation. This reaction involves a base-mediated transmetalation process, but the presence of a base also promotes competitive protodeborylation. Herein, we established a Suzuki–Miyaura cross-coupling reaction via Lewis acid-mediated transmetalation of an organopalladium(II) intermediate with organoborons. Experimental and theoretical investigations indicate that the controlled release of the transmetalation-active intermediate enables base-independent transmetalation under heating conditions and enhances the applicable scope of this process. This system enables us to avoid the addition of a traditional base and, thus, renders substrates with base-sensitive moieties available. Results from this research further expand the overall utility of cross-coupling chemistry.

Aryl Boronic Esters Are Stable on Silica Gel and Reactive under Suzuki–Miyaura Coupling Conditions

“…Aryl boronic acid derivatives are widely used to synthesize biaryl compounds that are the building blocks of many biologically active compounds, organic materials, and fine chemicals, using Suzuki–Miyaura coupling chemistry. , However, free aryl boronic acids are associated with several drawbacks. First, the carbon–boron (C–B) bond in an ArB­(OH) 2 often cleaves during functional group transformations.…”

“…Third, determining the structure of an ArB­(OH) 2 is sometimes complicated as it tends to undergo spontaneous partial dehydration to the corresponding boroxine. Consequently, a wide variety of ArB­(OH) 2 protecting groups have been developed to overcome these challenges. , …”

Size-Selective Suzuki–Miyaura Coupling Reaction over Ultrafine Pd Nanocatalysts in a Water-Stable Indium–Organic Framework

“…The formation of carbon–carbon bonds has long been regraded as one of the most prevalent and challenging methodologies in synthetic organic chemistry. , Among these strategies, Suzuki–Miyaura cross-coupling is recognized as the protagonist for the facile preparation of various asymmetric and symmetric biphenyl compounds that shows great significance in practical pharmaceutical applications. − In principle, the above coupling reaction proceeds conveniently with the addition of metal catalysts, among which palladium (Pd) is the most commonly used due to its high activity. , With this method, attaching Pd species to a heterogeneous carrier yields a catalyst that combines the advantages of homogeneous catalysis (catalytically active sites) and sustainable heterogeneous catalysis (high stability and convenient separation). Although many reports on Suzuki–Miyaura coupling over diverse Pd-based heterogeneous nanomaterials have been unveiled, − there is no report on well-designed catalysts with size-selective reaction to date .…”

Aryl Dance Reaction of Arylheteroles

“…For example, after the dance of 1a, addition of acyl chloride 5 promoted the Friedel-Crafts acylation, giving 6 in 88% yield, and the addition of NBS gave the bromo compound 7 in 85% yield. Furthermore, the addition of phenylboronic acid, palladium catalyst, and zinc catalyst after the addition of NBS allowed the Suzuki-Miyaura coupling reaction to proceed, yielding diarylbenzothiophene 11 The obtained 8 had its structure determined by X-ray analysis after recrystallization. It was also possible to react bromobenzothiophene 9 in arylation and aryl dance reactions in a one-pot process (Scheme 3C).…”