Recent Developments in the Suzuki–Miyaura Reaction Using Nitroarenes as Electrophilic Coupling Reagents

Lou Rocard,Piétrick Hudhomme

doi:10.3390/catal9030213

Abstract

Palladium-catalyzed cross-coupling reactions are nowadays essential in organic synthesis for the construction of C–C, C–N, C–O, and other C-heteroatom bonds. The 2010 Nobel Prize in Chemistry to Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki was awarded for the discovery of these reactions. These great advances for organic chemists stimulated intense research efforts worldwide dedicated to studying these reactions. Among them, the Suzuki–Miyaura coupling (SMC) reaction, which usually involves an organoboron reagent and an organic halide or triflate in the presence of a base and a palladium catalyst, has become, in the last few decades, one of the most popular tools for the creation of C–C bonds. In this review, we present recent progress concerning the SMC reaction with the original use of nitroarenes as electrophilic coupling partners reacting with the organoboron reagent.

Highlights

The importance of creating carbon–carbon (C–C) bonds in organic synthesis is demonstrated by the history of awardees of the Nobel Prize in Chemistry, for example, the Grignard reaction (1912), the Diels–Alder reaction (1950), the Wittig reaction (1979), and the olefin metathesis to Y
9, 213 of 8 compatible all kinds of C–B bonds, and alkyl, aryl, alkenyl and alkynylboronic acids or esters2 are able to participate as nucleophile partners in the palladium-catalyzed cross-coupling reaction [7,14]
Since the nitro group could be involved in the Pd-catalytic cycle, either as an electrophilic partner allowing oxidative addition, or as a nucleophile transmetallating with further reductive elimination, the utilization of nitroarenes in the Suzuki–Miyaura coupling (SMC) reaction has recently been investigated

Summary

Introduction

The importance of creating carbon–carbon (C–C) bonds in organic synthesis is demonstrated by the history of awardees of the Nobel Prize in Chemistry, for example, the Grignard reaction (1912), the Diels–Alder reaction (1950), the Wittig reaction (1979), and the olefin metathesis to Y. In the last few decades, transition metals have shown their ability to catalyze the formation of C–C single bonds and, among them, palladium-catalyzed reactions have been rapidly shown to be very efficient in organic chemistry [1]. Among the different metal-catalyzed cross-coupling reactions, the Suzuki–Miyaura coupling (SMC) reaction rapidly became one of the most efficient processes for the construction of C–C bonds, due to its high versatility, efficiency, and non-toxicity, making it suitable for industry [3] This cross-coupling is conventionally performed using organic halide or triflate as an electrophilic partner, and an organoboron reagent as the nucleophile. Nitroarenes have been reported as new electrophilic counterparts and, in this review, we highlight these new developments around the SMC reaction

Discussion

General

Plausible

Conclusion