A Phosphine-Accelerated ArF鈥揅hloride Bond Activation Process by Palladium

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• 作者：Meital Orbach ; Olena V. Zenkina ; Yael Diskin-Posner ; Mark A. Iron ; Milko E. van der Boom
• 刊名：Organometallics
• 出版年：2013
• 出版时间：May 24, 2013
• 年：2013
• 卷：32
• 期：10
• 页码：3074-3082
• 全文大小：441K
• 年卷期：v.32,no.10(May 24, 2013)
• ISSN：1520-6041

文摘

We present a mechanistic study demonstrating selective Ar_f鈥揅l bond activation preceded by 畏² coordination of Pd(PEt₃)₂ to a C鈺怌 moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Ar_f鈥揅l bond is plausible, but an intermolecular reaction becomes dominant in the presence of PEt₃. The latter pathway is significantly enhanced, since PEt₃ promotes dissociation of Pd(PEt₃)₃ from the C鈺怌 moiety followed by activation of the Ar_f鈥揅l bond. Our observations also show that PEt₃ can be used to control reaction selectivity. The experimental observations are supported by density functional theory (DFT) calculations (at the SMD(toluene)-DSD-PBEP86/cc-pV(D+d)Z-PP//DF-PBE+d_v2/SDD(d) level of theory).