Regioselective Nucleophilic Aromatic Substitution Reaction of meso-Pentafluorophenyl-Substituted Porphyrinoids with Alcohols
Regioselective Nucleophilic Aromatic Substitution Reaction of meso-Pentafluorophenyl-Substituted Porphyrinoids with Alcohols
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DOI：
10.1002/ejoc.201403503
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发表时间：
2015-03-01
影响因子：
2.8
通讯作者：
Wiehe, Arno
中科院分区：
文献类型：
--
作者：
Golf, Hartwig R. A.;Reissig, Hans-Ulrich;Wiehe, Arno
详细研究了meso-五氟苯基取代四吡咯与不同醇的亲核芳香取代反应。各种醇和碱在两种不同的溶剂中的系统调查导致优化的反应条件，允许选择性取代的p-氟原子的meso-五氟苯基取代的卟啉，它们的锌络合物，和meso-三（五氟苯基）corrole与醇和一个简单的碱在高产率。当与合适的保护基团组合应用于A（3）B卟啉时，可以在简单的两步一锅法中制备官能化的极性A（3）B卟啉。利用芳香亲核取代反应合成了二聚卟啉体系。此外，适当官能化的meso-五氟苯基取代的卟啉的铜（I）催化的1，3-偶极环加成导致相应的卟啉二聚体与1，2，3-三唑连接。本文所述的方法允许基于内消旋-五氟苯基取代的四吡咯的多官能化卟啉类化合物的简单且快速的方法。
A detailed study of the nucleophilic aromatic substitution reaction of meso-pentafluorophenyl-substituted tetrapyrrole systems with different alcohols is presented. The systematic investigation of various alcohols and bases in two different solvents led to optimized reaction conditions, allowing the selective substitution of the p-fluorine atoms of meso-pentafluorophenyl-substituted porphyrins, their zinc complexes, and a meso-tris(pentafluorophenyl) corrole with alcohols and a simple base in high yields. When applied to A(3)B porphyrins in combination with suitable protecting groups, functionalized, polar A(3)B porphyrins can be prepared in a simple two-step one-pot procedure. By using the nucleophilic aromatic substitution reaction, a dimeric porphyrin system was synthesized. In addition, the copper(I)-catalyzed 1,3-dipolar cycloaddition of properly functionalized meso-pentafluorophenyl-substituted porphyrins led to the corresponding porphyrin dimer with a 1,2,3-triazole linker. The method described herein allows a simple and fast approach towards multifunctionalized porphyrinoids based on meso-pentafluorophenyl- substituted tetrapyrroles.