Regioselective oxidation and metalation of meso-unsubstituted azuliporphyrins.

@article{Adiraju2016RegioselectiveOA,
  title={Regioselective oxidation and metalation of meso-unsubstituted azuliporphyrins.},
  author={Venkata A K Adiraju and Gregory M Ferrence and Timothy D Lash},
  journal={Organic \& biomolecular chemistry},
  year={2016},
  volume={14 44},
  pages={
          10523-10533
        }
}
Azuliporphyrins are intriguing porphyrin analogues that incorporate an azulene ring in place of a pyrrolic unit. This system undergoes regioselective oxidation reactions and favors the formation of stable organometallic derivatives. Reaction of meso-unsubstituted azuliporphyrins with Co2(CO)8 or CoCl2·6H2O gave 21-oxyazuliporphyrins, while Cu(OAc)2 produced the corresponding copper(ii) complexes. Treatment of an oxyazuliporphyrin with Ni(OAc)2 or Pd(OAc)2 afforded analogous nickel(ii) and… Expand
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References

SHOWING 1-10 OF 36 REFERENCES
Rhodium(III) Azuliporphyrins
The organometallic chemistry of azuliporphyrins has been extended to the first syntheses of rhodium(III) derivatives. Reaction of [Rh(CO)2Cl]2 with an azuliporphyrin in refluxing xylenes gaveExpand
Organometallic chemistry of azuliporphyrins: synthesis, spectroscopy, electrochemistry, and structural characterization of nickel(II), palladium(II), and platinum(II) complexes of azuliporphyrins.
TLDR
The straightforward synthesis of metalloazuliporphyrins under mild conditions, and their interesting spectroscopic, electrochemical, and structural features, demonstrates that the azulipoiryrin system holds great promise as a platform for organometallic chemistry. Expand
Synthesis, structural characterization and reactivity of heteroazuliporphyrins.
TLDR
A series of hetero-azuliporphyrins prepared by the "3 + 1" variant on the MacDonald condensation have significant diatropic character that is enhanced by the presence of an electron-donating tert-butyl substituent. Expand
Synthesis, spectroscopy, and reactivity of meso-unsubstituted azuliporphyrins and their heteroanalogues. Oxidative ring contractions to carba-, oxacarba-, thiacarba-, and selenacarbaporphyrins.
This paper reports the first detailed study on meso-unsubstituted azuliporphyrins, an important family of porphyrin-like molecules where one of the usual pyrrole rings has been replaced by an azuleneExpand
Synthesis and reactivity of N-methyl and N-phenyl meso-unsubstituted N-confused porphyrins.
TLDR
This study demonstrates that meso-unsubstituted NCPs have unusual reactivity and unique spectroscopic properties, and these results complement and extend the work on the much better known meso -tetraaryl NCP's. Expand
Synthesis and reactivity of carbachlorins and carbaporphyrins.
TLDR
The proton NMR spectrum showed that the carbachlorin is highly diatropic, and this has been confirmed by nucleus independent chemical shift (NICS) calculations. Expand
Further Studies on the Synthesis of meso‐Tetraarylazuliporphyrins under Lindsey−Rothemund Reaction Conditions and Their Conversion into Benzocarbaporphyrins
Azulene has been shown to react with pyrrole and a series of aromatic aldehydes in the presence of boron trifluoride etherate to give meso-tetraarylazuliporphyrins 6. Good yields of azuliporphyrinsExpand
Syntheses and reactivity of meso-unsubstituted azuliporphyrins derived from 6-tert-butyl- and 6-phenylazulene.
TLDR
A series of six azuliporphyrins with substituents on the seven-membered ring were prepared by two different "3 + 1" routes from 6-tert-butyl- and 6-phenylazulene, and analysis of the bond lengths suggests that a 17 atom delocalization pathway significantly contributes to the aromatic properties of this system. Expand
Adaptation of the Rothemund reaction for carbaporphyrin synthesis: preparation of meso-tetraphenylazuliporphyrin and related benzocarbaporphyrins.
TLDR
This work develops a "one-pot" Rothemund-type synthesis of meso-tetraphenylazuliporphyrin 7a, a group of cross-conjugated carbaporphyrinoids that exhibit intriguing chemistry and metallation properties that have previously only been available by multistep syntheses. Expand
Regioselective oxidations of benzocarbaporphyrins with ferric chloride: a facile synthesis of bridged [18]annulene ketals with strong absorptions in the far red and an unexpected halogenation reaction at the interior carbon atom.
TLDR
Benzocarbaporphyrins 4 were found to undergo regioselective oxidations with ferric chloride in methanol, ethanol, isopropyl alcohol, or ethylene glycol to give bridged benzo[18]annulene ketal derivatives 5 in excellent yields and mechanisms are proposed to explain the formation of these unusual oxidation products. Expand
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