Synthesis of ,β-Fused Thiazinamine-Porphyrins Oxidative C-N Fusion of Pyrimidinyl-Substituted Porphyrins.

5,15-Bis(pyrimidin-2-ylthio)porphyrins have been synthesized. Their electrochemical oxidation leads to the formation of mono- and bis-C-N-fused thiopyrimidinium intermediates depending on the applied charge and potential. These latter undergo nucleophilic attack with water during workup that drives the ring opening of the pyrimidinium moiety.

Stepwise Oxidative C-C Coupling and/or C-N Fusion of Zn(II) -Pyridin-2-ylthio-porphyrins.

The synthesis and characterization of zinc(II) -pyridin-2-ylthio-porphyrins are presented in this manuscript. The (electro)chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(-tolyl)-15-phenylporphyrinato] zinc(II) or [5,15-bis(pyridin-2-ylthio)-10,20-bis(-tolyl)porphyrinato] zinc(II) leads to the formation of one or two C-N bond(s) by intramolecular nucleophilic attack of the peripheral thiopyridinyl fragment(s) on the neighboring β-pyrrolic position(s) (C-N fusion reaction). In addition, the chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(-tolyl)porphyrinato] zinc(II), , bearing one free position, mainly affords the ,-dimer.

Regioselective C-H amination of free base porphyrins via electrogenerated pyridinium-porphyrins and stabilization of easily oxidized amino-porphyrins by protonation.

Four free base aminoporphyrins were synthesized in two steps via regioselective anodic nucleophilic substitution with pyridine followed by ring opening of the electrogenerated pyridinium with piperidine. The X-ray crystallographic structure of the unstable 2-aminotetraphenylporphyrin was solved. Protonation of this latter compound leads to the stable diiminium porphyrin salt.

Oxidative C-N fusion of pyridinyl-substituted porphyrins.

The mild (electro)chemical oxidation of pyridin-2-ylthio-meso substituted Ni(ii) porphyrins affords C-N fused cationic and dicationic pyridinium-based derivatives. These porphyrins are fully characterized and the molecular structure of one of them was confirmed by X-ray crystallography. A mechanism for the intramolecular oxidative C-N coupling is proposed based on theoretical calculations and cyclic voltammetry analyses.