Details

Autor(en) / Beteiligte

• Sharma, Meenakshi
• Banerjee, Subhadeep
• Zeller, Matthias
• Brückner, Christian

Titel

Fusion and Desulfurization Reactions of Thiomorpholinochlorins

Ist Teil von

• Journal of organic chemistry, 2016-12, Vol.81 (24), p.12350-12356

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2016

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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.