Decarbonylative organoboron cross-coupling of esters by nickel catalysis.

Kei Muto,Djamaladdin G Musaev,Junichiro Yamaguchi,Kenichiro Itami

doi:10.1038/ncomms8508

Kei Muto, Djamaladdin G Musaev + Show 2 more

Open Access

https://doi.org/10.1038/ncomms8508

Copy DOI

Journal: Nature communications	Publication Date: Jun 29, 2015
Citations: 239	License type: CC BY 4.0

Affiliation: Emory University, Nagoya University

Abstract

The Suzuki–Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. Herein, we report a significant advance in the choice of electrophilic coupling partner in this reaction. With a user-friendly and inexpensive nickel catalyst, a range of phenyl esters of aromatic, heteroaromatic and aliphatic carboxylic acids react with boronic acids in a decarbonylative manner. Overall, phenyl ester moieties function as leaving groups. Theoretical calculations uncovered key mechanistic features of this unusual decarbonylative coupling. Since extraordinary numbers of ester-containing molecules are available both commercially and synthetically, this new ‘ester' cross-coupling should find significant use in synthetic chemistry as an alternative to the standard halide-based Suzuki–Miyaura coupling.

Highlights

The Suzuki–Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule
The Suzuki–Miyaura coupling, a palladium- or nickelcatalysed cross-coupling reaction of boron-based nucleophiles and organic electrophiles[1,2], is one of the most reliable reactions in synthetic organic chemistry, indispensable in the synthesis of a range of functional organic materials ranging from pharmaceuticals, agrochemicals, organic electronic devices and liquid crystals (Fig. 1a)
Subsequent reductive elimination releases the decarbonylative cross-coupling product and regenerates Ni0 species. Armed by these knowledge and the discovered beneficial impact of a phenyl substituent on the cleavage of C(acyl)–O bonds by nickel catalysts[22,25], we primarily focused on the use of phenyl esters of arenecarboxylic acids (ArCO2Ph) in this study

Summary

Introduction

The Suzuki–Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. We describe a rare example of the unconventional use of esters as the electrophilic component in a nickel-catalysed Suzuki–Miyaura cross-coupling. Gooen et al.[15] reported that aromatic carboxylic acids and haloarenes could be cross-coupled in a decarboxylative manner employing a palladium-copper bimetallic catalytic system. Phthalimides react in a similar manner with diorganozinc reagents, but this reaction requires a stoichiometric amount of nickel complex[20]

Methods

Results

Conclusion