Citation: REN Qing-Hua, SHEN Xiao-Yan. Reaction Mechanism for the Iron-Catalyzed Biaryl Cross-Coupling of Aryl Grignard Reagents[J]. Acta Physico-Chimica Sinica, ;2015, 31(5): 852-858. doi: 10.3866/PKU.WHXB201503026 shu

Reaction Mechanism for the Iron-Catalyzed Biaryl Cross-Coupling of Aryl Grignard Reagents

1.
Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. China

Received Date: 25 December 2014
Available Online: 2 March 2015
Fund Project: 项目(B.58-B111-12-101, B.58-B111-12-103)资助 (B.58-B111-12-101, B.58-B111-12-103)

Mechanisms for the [Fe(MgBr)₂] catalyzed cross-coupling reaction between ortho-chlorostyrene and phenylmagnesium bromide to form biaryl were studied using density functional theory (DFT) calculations. We investigated two mechanisms. Cycle A included three basic steps: (I) oxidation of [Fe(MgBr)₂] to obtain [Ar- Fe(MgBr)], (II) addition to yield [Ar-(phenyl)-Fe(MgBr)₂], and (III) reductive elimination to return to [Fe(MgBr)₂]. Cycle B did not form [Ar-Fe(MgBr)]. In the first step, phenylmagnesium bromide attacks the intermediate of the oxidative addition directly before [Cl-Mg-Br] dissociates to form [Ar-Fe(MgBr)]. The catalytic Cycle B is favored over the catalytic Cycle Awhen considering the solvent effect. The rate-limiting step in the overall catalytic cycle for both Cycle A and Cycle B is the reductive elimination of [Ar-(phenyl)-Fe(MgBr)₂] to regenerate the catalyst [Fe(MgBr)₂], where the Gibbs free energy in solvent tetrahydrofuran (THF), ΔG_sol, is 82.98 kJ ·mol^-1, as determined using the conductor polarized continuum model (CPCM) method.
- Iron catalyst,
- Biaryl,
- Cross-coupling,
- Reaction mechanism,
- Density functional theory
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