DFT Study on Mechanism of Pd(OAc)2-Catalyzed C-C Coupling reaction

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  The Pd(OAc)2-Catalyzed C-C Cross-Coupling reaction mechanism of 3-methoxyacetanilide with n-butyl acrylate in presence of HBF4 and additives has been investigated,using density functional theory(DFT)calculations at the B3LYP level.The catalyst cycle proceeds through four main steps involving C-H activation,alkene insertion,β-hydride elimination,and recycling of catalyst.It is found that the C-H activation step is the rate-determining step over the whole reactions and in C-H activation step,the six-member pathway is the favorable path.In alkene insertion and β-hydride elimination steps,HBF4 decomposes slowly in aqueous solution(HBF4 + H2O→BF3OH-+ H+ + HF)and provide a source of HF to accelerate the processes.In addition,it is shown that water as solvent does not change the general trends for the reaction potential energy surface.
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