Mechanism and Stereoselectivity of Directed C(sp3)–H Activation and Arylation Catalyzed by Pd(II) with Pyridine Ligand and Trifluoroacetate: A Computational Study
作者： Julong Jiang , Jin-Quan Yu , Keiji Morokuma
DOI: 10.1021/CS501626N
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摘要: Density functional theory (DFT) calculations were conducted to elucidate the mechanism of a novel Pd(II) catalyzed C(sp3)–H activation and subsequent arylation reactions amides in presence pyridine derivatives as ligands. All plausible pathways carefully studied, minimum energy pathway was located successfully. Being different from most C–H reactions, 2-picoline used this reaction reacts with Pd(TFA)2 (trifluoroacetate) form very stable precatalyst. Measures should thus be taken activate precatalyst, including modification amide substrate proper choice solvent. Our helped reveal relevant details. An unconventional deprotonation for step, which is traditional CMD (or AMLA) mechanism, found through our theoretical studies. The methyl group deprotonated by an out-of-plane (external) TFA, rather than TFA ligand directly bound atom. As part o...
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