The Murai reaction is a ruthenium-catalyzed transformation leading to alkylated arenes through the C−C bond formation between an alkene and an arene bearing a directing group. Discovered in the nineties, this useful C−H activation based coupling has been the object of intense study since its discovery. After having studied the Murai reaction on 2-formylfurans of biomass derivation, we describe here the carbonylative version applied to 2-formylfurans, 2-formylpyrrols and 2-formylthiophenes. This acylation reaction takes place regioselectively at C3 position of the heterocyclopentadienes thanks to the installation of removable imine directing groups. The transformation can be achieved by treating the two reaction partners with a catalytic amount of Ru3(CO)12, in toluene at 120–150 °C, after CO bubbling, at atmospheric pressure. DFT computations of the full catalytic cycle help in deciphering the mechanism of this transformation, and to rationalize the different behaviors depending on the nature of imine directing groups. (Figure presented.).

Ru-Catalyzed Carbonylative Murai Reaction: Directed C3-Acylation of Biomass-Derived 2-Formyl Heteroaromatics

Broggini G.;
2020

Abstract

The Murai reaction is a ruthenium-catalyzed transformation leading to alkylated arenes through the C−C bond formation between an alkene and an arene bearing a directing group. Discovered in the nineties, this useful C−H activation based coupling has been the object of intense study since its discovery. After having studied the Murai reaction on 2-formylfurans of biomass derivation, we describe here the carbonylative version applied to 2-formylfurans, 2-formylpyrrols and 2-formylthiophenes. This acylation reaction takes place regioselectively at C3 position of the heterocyclopentadienes thanks to the installation of removable imine directing groups. The transformation can be achieved by treating the two reaction partners with a catalytic amount of Ru3(CO)12, in toluene at 120–150 °C, after CO bubbling, at atmospheric pressure. DFT computations of the full catalytic cycle help in deciphering the mechanism of this transformation, and to rationalize the different behaviors depending on the nature of imine directing groups. (Figure presented.).
ADVANCED SYNTHESIS & CATALYSIS
carbonylation; C−H activation; homogeneous catalysis; Murai reaction; ruthenium
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11383/2095406
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