Synthesis of trans-A2B2-Porphyrins Bearing Phenylethynyl Substituents
Synthesis of trans-A2B2-Porphyrins Bearing Phenylethynyl Substituents
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DOI：
10.1021/jo1025578
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发表时间：
2011-04-15
影响因子：
3.6
通讯作者：
Gryko, Daniel T.
中科院分区：
文献类型：
--
作者：
Nowak-Krol, Agnieszka;Koszarna, Beata;Gryko, Daniel T.
本文报道了由不同亲脂性和反应活性的苯炔醛和二吡咯甲烷直接合成带有两个苯乙炔基的反式-A（2）B（2）-卟啉的有效和方便的条件。这种新的程序允许制备具有广泛取代基的这种结构的卟啉库。由于确定了试剂溶解度是影响卟啉原产率的关键因素之一，我们能够将产率提高到约10%。百分之三十两组条件的范围和限制进行了探讨。这种方法的方法学优点是其直接获得结构单元和在最后一步中形成卟啉核，而不需要三键的脱保护或溴化和连续的偶联反应，这通常需要铜盐来顺利进行，特别是与缺电子的炔合作伙伴。因此，它防止了不希望的铜卟啉形成，以及需要使用昂贵的炔。还改进了制备苯基炔醛的两步法。
Efficient and convenient conditions for the preparation of trans-A(2)B(2)-porphyrins bearing two phenylethynyl moieties directly from phenylpropargyl aldehydes and dipyrromethanes of diversified lipophilicity and reactivity have been developed. This new procedure allows the preparation of a library of porphyrins of this architecture with a wide range of substituents. Thanks to the identification of the reagent solubility as one of the key factors influencing the yield of the porphyrinogens, we were able to improve yields to ca. 30%. The scope and limitations of two sets of conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in the last step without the need for deprotection of the triple bond or bromination and consecutive coupling reaction, which often demands copper salts to proceed smoothly, especially with electron-deficient alkyne partners. Therefore, it prevents undesired copper porphyrin formation, as well as the need for utilizing expensive alkynes. A two-step method for the preparation of phenylpropargyl aldehydes has also been refined.