Synthesis of Peripherally Annulated Phenanthroporphyrins
Synthesis of Peripherally Annulated Phenanthroporphyrins
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外周环状菲卟啉的合成
DOI：
10.1021/acs.orglett.3c00876
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发表时间：
2023
期刊：
影响因子：
5.2
通讯作者：
Kobayashi Nagao
中科院分区：
文献类型：
--
作者：
Muramatsu Kota;Okujima Tetsuo;Mori Shigeki;Kikuchi Shion;Ando Shimpei;Okada Yusuke;Takase Masayoshi;Uno Hidemitsu;Kobayashi Nagao
采用分步前驱体法合成了不常见的菲咯啉化合物。前体卟啉与芳基取代的双环[2.2.2]辛二烯通过逆向Diels-Alder反应得到相应的芳基苯并卟啉(ArylBPs)。通过芳基BPs的分子内Scholl反应得到了不寻常的菲咯啉。X射线结晶学分析显示，它是一个扭曲的螺旋状的卟啉平面。观察到四苯基卟啉在B带的红移吸收在580 nm，Q带的红移吸收在700-900 nm。用磁性圆二色谱分析和含时密度泛函理论计算对其光学性质和电子结构进行了解释。
Synthesis of unusual phenanthroporphyrins was achieved by a stepwise precursor method. Precursor porphyrins fused with aryl-substituted bicyclo[2.2.2]octadiene afforded the corresponding arylbenzoporphyrins (arylBPs) by a retro Diels–Alder reaction. Unusual phenanthroporphyrins were obtained via the intramolecular Scholl reaction of arylBPs. X-ray crystallographic analysis revealed a distorted, helical porphyrin plane. Red-shifted absorptions of tetraphenanthroporphyrin are observed at ca. 580 nm for the B band and at 700–900 nm for the Q bands. Analysis of magnetic circular dichroism spectra and time-dependent density functional theory calculations was used to explain the optical properties and electronic structures.