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A new synthesis of porphyrins via a putative trans-manganese(iv)-dihydroxide intermediate.
Dalton Transactions ( IF 4 ) Pub Date : 2020-01-09 , DOI: 10.1039/c9dt03573g
Sruti Mondal 1 , Kasturi Sahu , Bratati Patra , Subhrakant Jena , Himansu S Biswal , Sanjib Kar
Affiliation  

A new method for the synthesis of meso-substituted porphyrins was developed. In this two-step methodology, the first step involves the condensation of pyrroles/dipyrromethanes with aldehydes in a water-methanol mixture under acidic conditions. The second step involves manganese induced cyclization followed by oxidation via PhIO/O2. This methodology has been useful for the synthesis of a wide range of trans-A2B2 porphyrins and also symmetric porphyrins in moderate to good yields. A detailed investigation of the manganese induced cyclization reaction has allowed us to characterize a Mn-porphyrinogen complex. A series of analytical and spectroscopic techniques and DFT calculations have led us to the conclusion that the putative intermediate species are trans-manganese(iv)-dihydroxide complexes. EPR and magnetic susceptibility measurements helped us to assign the oxidation state of the manganese complexes in their native state. The assumption of trans-manganese(iv)-dihydroxide as the true intermediate for this porphyrin synthesis has been authenticated via in situ UV-Vis experiments. This new methodology is certainly different from other previously reported methodologies in many aspects and most importantly these reactions can be easily performed on a gram scale for the synthesis of porphyrins.

中文翻译:

通过推定的反式锰(iv)-二氢氧化物中间体合成卟啉的新方法。

开发了一种新的合成介孔取代卟啉的方法。在此两步方法中,第一步涉及在酸性条件下,将吡咯/二吡咯甲烷与醛在水-甲醇混合物中进行缩合。第二步涉及锰诱导的环化反应,然后通过PhIO / O2进行氧化。该方法已用于以中等到良好的产率合成各种反式A2B2卟啉以及对称卟啉。对锰诱导的环化反应的详细研究使我们能够表征Mn-卟啉原复合物。一系列分析和光谱技术以及DFT计算得出的结论是,假定的中间物种是反式锰(iv)-二氢氧根配合物。EPR和磁化率测量帮助我们确定了天然状态下锰配合物的氧化态。已经通过原位UV-Vis实验验证了反式锰(iv)-二氢氧化物作为该卟啉合成的真正中间体的假设。这种新方法肯定在许多方面与其他先前报道的方法不同,最重要的是,这些反应可以很容易地以克为单位进行卟啉的合成。
更新日期:2020-02-10
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