Department of Chemistry, University of Tromsø, N-9037, Tromsø, Norway.
Sci Rep. 2022 Nov 10;12(1):19256. doi: 10.1038/s41598-022-23889-0.
Boron tribromide-mediated demethylation of rhenium-oxo and gold meso-tris(4-methoxyphenyl)corrole and meso-tris(3,5-dimethoxyphenylcorrole), M[TpOMePC] and M[T(3,5-OMe)PC] (M = ReO, Au), have yielded the corresponding phenol- and resorcinol-appended metallocorroles, M[TpOHPC] and M[T(3,5-OH)PC], in good yields. The latter compounds proved insoluble in dichloromethane and chloroform but soluble in THF. The M[T(3,5-OH)PC] derivatives also proved moderately soluble in 0.05 M aqueous KOH. Unlike oxidation-prone aminophenyl-substituted corroles, the phenol- and resorcinol-appended metallocorroles could be readily handled in air without special precautions. The phenolic metallocorroles could be readily alkylated with 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl iodide ("FtI") to afford the fluorous-tagged metallocorroles M[TpOFtPC] and M[T(3,5-OFt)PC] in > 90% yields. The simplicity of the synthetic protocols promise a wide range of phenolic and fluorous-tagged porphyrin analogues with potential applications to diverse fields such as sensors, catalysis, and photodynamic therapy, among others.
三溴化硼介导的铼氧和金中-三（4-甲氧基苯基）卟啉和中-三（3,5-二甲氧基苯基）卟啉（M[TpOMePC]和 M[T(3,5-OMe)PC]（M = ReO，Au）的脱甲基化反应，产率良好地生成了相应的酚基和间苯二酚取代的金属卟啉，M[TpOHPC]和 M[T(3,5-OH)PC]。后两种化合物在二氯甲烷和氯仿中不溶，但在 THF 中可溶。M[T(3,5-OH)PC]衍生物在 0.05 M 稀 KOH 中也具有中等溶解度。与易氧化的氨苯基取代卟啉不同，酚基和间苯二酚取代的金属卟啉可以在空气中无需特殊预防措施即可轻松处理。酚基金属卟啉可以很容易地与 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-十七氟十一烷基碘化物（“FtI”）烷基化，以> 90%的产率得到氟标记的金属卟啉 M[TpOFtPC]和 M[T(3,5-OFt)PC]。合成方案的简单性有望实现广泛的酚基和氟标记的卟啉类似物，它们在传感器、催化、光动力疗法等多个领域具有潜在应用。
