Suzuki coupling catalyzed by chloro({2-[mesityl(quinolin-8-yl-κN)boryl]-3,5-dimethylphenyl}methyl-κC)palladium(II)

TETRAHEDRON

卷:75

Article

Tamang, Sem Raj¹  Achazi, Andreas J.¹  Rust, Haley S.¹  Dhungana, Pramod¹  Miro, Pere¹  Hoefelmeyer, James D.¹ 

[1] Univ South Dakota, Dept Chem, 414 E Clark St, Vermillion, SD 57069 USA

关键词: Ambiphilic ligand;    Palladium;    Catalysis;    Suzuki;    DFT;   

DOI  :  10.1016/j.tet.2019.03.001

来源: Elsevier

【 摘 要 】

The title compound was evaluated as catalyst for Suzuki coupling of aryl halides (X = I, Br) with phenylboronic acid at room temperature. The rates of the reactions increase with increasing Hammet sigma constant of m-substituents on the arylhalide. The presence of ortho groups on the arylhalides had the effect of lowering the reaction rates. Density functional theory study of the mechanism for the formation of a Pd-(0) complex from the title molecule was performed. Reductive elimination of chloride and the eta(4)-BCCC moiety was endergonic and ruled out as a likely pathway. Instead, conversion of the title molecule to phenyl({2-[mesityl(quinolin-8-yl-kappa N)boryl]-3,5-dimethylphenyl}methyl-kappa C)palladium(II) complex is thermodynamically favored and predicted to further react with the solvent and the Suzuki coupling reagents to undergo reductive elimination of diphenyl to form a reactive Pd-(0) complex. (C) 2019 Elsevier Ltd. All rights reserved.

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