BIII-Subporphyrins Bearing Distorted Metal-Coordinating Straps: CuII-Assisted meso-Fabrications
Zhenjing Luo1, Boyu Xiao1, Ling Xu1
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China. Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province. College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China.
Abstract:
BIII-subporphyrins 4, 5, and 6 possessing metal-coordinating carbaporphyrin-like pockets were synthesized by Suzuki-Miyaura coupling reactions. Compounds 4 and 5 gave PdII complexes 4-Pd and 5-Pd upon metalation with Pd(OAc)2 but did not give either their NiII or CuII complexes. Conversely, 6 was expected to induce distorted square planar coordination because of its 2,5-di(pyrid-2-yl)pyrrole strap. Indeed reaction of 6 with Cu(OAc)2 did not give its CuII complex but produced meso-alkoxy and meso-phenoxy products in the presence of alcohols and phenol, possibly via CuII-mediated C-H bond functionalization, which was further extended to meso-C-C bond-forming fabrications by using organoboronic acids. These CuII-mediated C-H bond meso-fabrications are the first example for porphyrinoid substrates.
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