B-subporphyrins , , and possessing metal-coordinating carbaporphyrin-like pockets were synthesized by Suzuki-Miyaura coupling reactions. Compounds and gave Pd complexes and upon metalation with Pd(OAc) but did not give either their Ni or Cu complexes. Conversely, was expected to induce distorted square planar coordination because of its 2,5-di(pyrid-2-yl)pyrrole strap. Indeed reaction of with Cu(OAc) did not give its Cu complex but produced -alkoxy and -phenoxy products in the presence of alcohols and phenol, possibly via Cu-mediated C-H bond functionalization, which was further extended to -C-C bond-forming fabrications by using organoboronic acids. These Cu-mediated C-H bond -fabrications are the first example for porphyrinoid substrates.
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