Fusion and Desulfurization Reactions of Thiomorpholinochlorins.
Meenakshi SharmaSubhadeep BanerjeeMatthias ZellerChristian BrücknerPublished in: The Journal of organic chemistry (2016)
An unusually nonplanar, ruffled structure that had been suspected for the previously reported [2,3-bismethylenethiomorpholinochlorinato]nickel(II) complex was confirmed by determination of its crystal structure. Treatment of this thiomorpholinochlorin with acid converts the exocyclic double bonds to direct links to the ortho-positions of both adjacent meso-phenyl groups. The crystal structure of this product indicated that the introduction of these linkages did not change the overall conformation of the macrocycle. The reactivity of the bis-linked thiomorpholine moiety with respect to Raney-nickel-induced (hydro)desulfurization reactions was probed, forming a bis-phenyl-linked 2,3-dimethylchlorin, also characterized by X-ray diffraction, and a bis-indene-annulated porphyrin. We also report on the synthesis of the oxygen analogue to the bis-linked thiomorpholine by reaction of a secochlorin bisketone nickel complex with Woollins' reagent. We thus introduce novel methodologies toward the synthesis of porphyrinoids carrying β-to-ortho-phenyl fusions and expand on the scope and limits of the chemistry and interconversion of pyrrole-modified porphyrins.
Keyphrases
- crystal structure
- ionic liquid
- metal organic framework
- reduced graphene oxide
- oxide nanoparticles
- photodynamic therapy
- high glucose
- molecular dynamics simulations
- high resolution
- pulmonary embolism
- diabetic rats
- oxidative stress
- computed tomography
- solid phase extraction
- gold nanoparticles
- combination therapy
- electron microscopy
- endothelial cells
- liquid chromatography
- tandem mass spectrometry