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

The synthesis and characterization of zinc(II) meso-pyridin-2-ylthio-porphyrins are presented in this manuscript. The (electro)chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(p-tolyl)-15-phenylporphyrinato] zinc(II) or [5,15-bis(pyridin-2-ylthio)-10,20-bis(p-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 ß-pyrrolic position(s) (C-N fusion reaction). In addition, the chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(p-tolyl)porphyrinato] zinc(II), i.e., bearing one free meso position, mainly affords the meso,meso-dimer. Further stepwise electrochemical oxidation selectively produces the mono and bis C-N fused meso,meso-dimer. The resulting pyridinium derivatives exhibit important changes in their physicochemical properties (NMR, UV-vis, CV) as compared to their initial unfused precursors. Also, the X-ray crystallographic structures of three unfused monomers, one unfused meso,meso-dimer, and two C-N fused monomers are presented.

Synthesis of meso,ß-Fused Thiazinamine-Porphyrins via 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. When piperidine is added before or after workup, the neutral fused porphyrinthiazin-2-amines are generated, and they exhibit a significant bathochromic shift of their Soret and Q bands.

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.