Stoichiometric and Catalytic Aryl–Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes

This Communication describes studies of Ph–RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)­PdII(Ph)­(RF). The CF3 analogue participates in fast Ph-CF3 coupling (II complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd­(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.

本研究通讯报道了针对结构通式为(PtBu3)PdII(Ph)(RF)的钯配合物所开展的Ph–RF偶联反应研究，其中RF代表CF3或CF2CF3，Ph为苯基。三氟甲基取代的对应配合物可发生快速的Ph-CF3偶联反应（涉及II型配合物）。此外，研究表明将配体从CF3替换为CF2CF3，可规避该非目标反应路径。最终，通过化学计量研究所获得的认知，成功鉴定出二(三叔丁基膦)合钯（Pd(PtBu3)2）可作为催化剂，用于催化芳基溴化物与三甲基硅基五氟乙基（TMSCF2CF3）的钯催化交叉偶联反应，以制备五氟乙基化芳烃。