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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Metalations of a Carbazole-Incorporated N-Confused Porphyrin
Jiale Tang1, Yutao Rao1, Mingbo Zhou1
1Key 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:
A carbazole-incorporated N-confused porphyrin (NCP) 3 was synthesized via a Suzuki-Miyaura cross-coupling strategy and exhibits solvent-dependent 2H/3H tautomerism. Metalation studies revealed distinct metal-dependent reactivity: Ag+ afforded the planar Ag3+ complex 3-Ag, whereas Pd2+ selectively formed the cis-PdCl2-bridged dimer 4 through outer-nitrogen coordination. In contrast, Cu2+ induced diverse oxidative transformations. Initial formation of 3-Cu was followed by oxygen insertion and ring oxidation to generate unprecedented structures, including a Cu-C-C three-membered motif (6) and 4,5-dioxygenated 2-pyrrolidone units (7). Isotopic labeling experiments established CHCl3 as the carbon source of the formyl group. Spectroscopic analyses revealed pronounced structure-property correlations governed by the coordination geometry and π conjugation.
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