A Phosphine-Accelerated Ar-F-Chloride Bond Activation Process by Palladium

作者：Orbach Meital; Zenkina Olena V; Diskin Posner Yael; Iron Mark A; van der Boom Milko E^*

来源：Organometallics, 2013, 32(10): 3074-3082.

DOI：10.1021/om400295p

We present a mechanistic study demonstrating selective Ar-f-Cl bond activation preceded by eta(2) coordination of Pd(PEt3)(2) to a C=C moiety of a partially fluorinated substrate. An intramolecular ring-walking process to activate the Ar-f-Cl 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=C moiety followed by activation of the Ar-f-Cl 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).

• 出版日期2013-5-27