Thermal fusion reactions of meso-(3-thienyl) groups in [26]hexaphyrins to produce Möbius aromatic molecules.
Thermal fusion reactions of meso-(3-thienyl) groups in [26]hexaphyrins to produce Möbius aromatic molecules.
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DOI：
10.1002/anie.200902677
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发表时间：
2009-08
影响因子：
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通讯作者：
M. Inoue;Kil Suk Kim;Masaaki Suzuki;Jong Min Lim;Jae‐Yoon Shin;Dongho Kim;A. Osuka
中科院分区：
文献类型：
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作者：
M. Inoue;Kil Suk Kim;Masaaki Suzuki;Jong Min Lim;Jae‐Yoon Shin;Dongho Kim;A. Osuka
π-电子共轭的拓扑学是当前结构有机化学的一个重要课题。[1]Herges等人的开创性论文促进了这个领域的发展。作为第一个稳定的Möbius芳香族分子，四苯并[16]轮烯的合成。[2]Möbius芳香性的概念是由海尔布朗纳在1964年首次提出的，[3]但由于实现光滑的共轭π网络和单个分子内的扭曲构象的结构要求，它的实现相当困难。Latos-Grazyn ski等人。报道了一种在低温下具有扭曲的Möbius构象的二对苯并[28]六氢呋喃。[5]我们发现，通过金属配位、[6a，b]温度控制、[6c，d]和质子化，中位芳基扩展的卟啉可以形成稳定的Möbius芳香分子。[6e]最近发现了一个额外的Möbius芳香体系，该体系是通过加热中六(五氟苯基)取代的[26]己醛在冰醋酸中合成的。
The topology of π-electronic conjugation is an important current topic in structural organic chemistry.[1] This area has been boosted by the seminal paper by Herges et al. on the synthesis of a tetrabenzo [16] annulene as the first stable Möbius aromatic molecule.[2] The concept of Möbius aromaticity was first suggested by Heilbronner in 1964,[3] but its realization has been quite difficult owing to the structural requirements of implementing a smooth conjugated π network and a twisted conformation within a single molecule.[4] Recently, expanded porphyrins, which are pyrrolic conjugated macrocycles, have emerged as a new promising class of molecules for creation of Möbius aromatic systems. Latos-Grazyn ski et al. reported a di-p-benzo [28] hexaphyrin that has a twisted Möbius conformation at low temperature.[5] We found that stable Möbius aromatic molecules were formed from meso-aryl expanded porphyrins by metal coordination,[6a, b] temperature control,[6c, d] and protonation.[6e] Recently an additional Möbius aromatic system was found upon heating of meso-hexakis (pentafluorophenyl)-substituted [26] hexaphyrin in acetic acid.[6f] Despite these efforts, Möbius aromatic molecules are still rare, and a new synthetic strategy to produce Möbius aromatic molecule is highly desirable.