Cu-Catalyzed Carbon-Heteroatom Coupling Reactions under Mild Conditions Promoted by Resin-Bound Organic Ionic Bases

Resin-bound organic ionic bases (RBOIBs) were developed in which tetraalkyl-ammonium or phosphonium cations are covalently attached to solid resins. The application tests showed that the performance of the tetraalkyl-ammonium-type RBOIBs is slightly better than that of the corresponding Cs salts in Cu-catalyzed C-N cross-couplings, while the tetraalkylphosphonium-type RBOIBs are significantly better than all the inorganic bases. With these newly developed RBOIBs, room-temperature Cu-catalyzed C-N coupling with various nonactivated aryl iodides and even aryl bromides can be readily accomplished. Moreover, RBOIBs can be easily recycled and reused for a number of times without much drop of activity. The good performances of RBOIBs are proposed to arise from the relatively weak binding forces between the cationic polymer backbone and basic anions, as opposed to the strong metal-anion interactions in the inorganic bases. Further applications of RBOIBs in Ni-catalyzed Suzuki-type couplings at room temperature, Cu-catalyzed C-N couplings at -30 degrees C, a Pd-catalyzed Heck reaction at 60 degrees C, and Cu-catalyzed C-S couplings at room temperature demonstrate that RBOIBs are generally applicable bases with improved performance for many other types of organic transformations.