Abstract

A carboranylporphyrin of A₃B-type bearing a single pentafluorophenyl ring was prepared through the regioselective nucleophilic aromatic substitution reaction of the p-fluorine atoms in 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with 9-mercapto-m-carborane. The reaction of this porphyrin with sodium azide led to the selective substitution of the p-fluorine atom in the pentafluorophenyl substituent with an azide functionality which upon reduction with SnCl₂ resulted in the formation of the corresponding porphyrin with an amino group. Pentafluorophenyl-substituted A₃B-porphyrins were studied and transformed to thiol and amino-substituted compounds allowing for the preparation of porphyrins with different reactive groups such as hydroxy and amino derivatives capable for further functionalization and conjugation of these porphyrins to other substrates. In addition, conjugates containing maleimide or biotin entities in the structure of carborane A₃B-porphyrin were also synthesized based on the amino-substituted A₃B-porphyrin. The structures of the prepared carboranylporphyrins were determined by UV–vis, IR, ¹H, ¹⁹F, ¹¹B NMR spectroscopic data and MALDI mass spectrometry.

Beilstein J. Org. Chem. 2024, 20, 767–776. doi:10.3762/bjoc.20.70

摘要

通过5,10,15,20-四(五氟苯基)卟啉中的对氟原子与9-巯基间碳硼烷发生区域选择性亲核芳香取代反应，制备了带有单个五氟苯环的A ₃ B型碳硼烷基卟啉。 。该卟啉与叠氮化钠的反应导致五氟苯基取代基中的对氟原子被叠氮化物官能团选择性取代，该叠氮官能团在用SnCl ₂还原时导致形成相应的带有氨基的卟啉。研究了五氟苯基取代的 A ₃ B-卟啉并将其转化为硫醇和氨基取代的化合物，从而可以制备具有不同反应基团的卟啉，例如羟基和氨基衍生物，能够进一步官能化这些卟啉并将其与其他底物缀合。此外，基于氨基取代的A _{3 B-卟啉还合成了碳硼烷A 3} B-卟啉结构中含有马来酰亚胺或生物素实体的缀合物。通过UV-vis、IR、 ¹ H、¹⁹ F、¹¹ B NMR 光谱数据和MALDI 质谱测定了所制备的碳硼烷基卟啉的结构。

贝尔斯坦 J. 组织。化学。 2024, 20, 767–776。 doi:10.3762/bjoc.20.70