ChemInform Abstract: Etherification of Functionalized Phenols with Chloroheteroarenes at Low Palladium Loading: Theoretical Assessment of the Role of Triphosphane Ligands in C-O Reductive Elimination.

ChemInform ◽  
2012 ◽  
Vol 43 (19) ◽  
pp. no-no
Author(s):  
Melanie Platon ◽  
Luchao Cui ◽  
Sophal Mom ◽  
Philippe Richard ◽  
Mark Saeys ◽  
...  
Keyword(s):  
Reductive Elimination ◽  
Theoretical Assessment

scholarly journals The Mechanism of Rhodium Catalyzed Allylic C–H Amination

2019 ◽  
Author(s):  
Robert Harris ◽  
Jiyong Park ◽  
Taylor Nelson ◽  
Nafees Iqbal ◽  
Daniel Salgueiro ◽  
...  
Keyword(s):  
Acid Catalyst ◽  
Reductive Elimination ◽  
Quantum Mechanical ◽  
Allylic Amination ◽  
Reaction Conditions ◽  
Allyl Complex ◽  
Acetate Ligand ◽  
Amination Reaction ◽  
Lewis Acid Catalyst

The mechanism of catalytic allylic C–H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate that allylic C–H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidant in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetry<b></b>experiments support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand. Lastly, evidences supporting the amination of an allylic acetate intermediate is presented. Both nucleophilic substitution catalyzed by Ag<sup>+</sup>that behaves as a Lewis acid catalyst and an inner-sphere amination catalyzed by Cp*Rh are shown to be viable for the last step of the allylic amination reaction.

On the Mechanism of the Nickel-Catalyzed Boron Insertion into the C−O Bond of Benzofuran

2019 ◽  
Author(s):  
Ana Mateo-Martínez ◽  
Hayate Saito ◽  
Hideki Yorimitsu ◽  
Carles Bo
Keyword(s):  
Reductive Elimination ◽  
Nucleophilic Attack ◽  
Dft Studies ◽  
Reaction Conditions ◽  
Elementary Steps

<p>The reaction of benzofurans with diboron reagents and Cs<sub>2</sub>CO<sub>3</sub>catalyzed by Ni(0) complexes results in the insertion of boron into the C-O bond. The reaction conditions mimic those reported by Martin and Hosoya for borylating aryl C-F bonds, but neither the role of the base nor the sequence of elementary steps is clear. Herein we report on the mechanism of such transformation on the basis of DFT studies, which suggest that the base activates the diboron reagent and generates a reactive boryl group, that Ni(II) is reduced back to Ni(0) during the boryl insertion into the Ni-O bond, and that the classical reductive elimination step is best viewed as a ring-contracting nucleophilic attack. </p>

C−C Reductive Elimination in Palladium Complexes, and the Role of Coupling Additives. A DFT Study Supported by Experiment

2009 ◽  
Vol 131 (10) ◽  
pp. 3650-3657 ◽  
Author(s):  
Martín Pérez-Rodríguez ◽  
Ataualpa A. C. Braga ◽  
Max Garcia-Melchor ◽  
Mónica H. Pérez-Temprano ◽  
Juan A. Casares ◽  
...  
Keyword(s):  
Reductive Elimination ◽  
Palladium Complexes ◽  
Dft Study
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