四硫 S-稠合异佛尔酮氧化转化为卟啉阳离子。
Oxidative Transformation of a Tetrathia S-Confused Isophlorin into Porphyrin Cation.
机构信息
Department of Chemistry, Indian Institute of Science Education and Research (IISER) , Pune 411008, Maharashtra, India.
出版信息
Org Lett. 2017 Sep 15;19(18):4854-4857. doi: 10.1021/acs.orglett.7b02317. Epub 2017 Sep 6.
The synthesis and redox properties of first generation S-confused isophlorins are described. Despite structural resemblance to a confused porphyrin, spectroscopic and computational studies reveal weak paratropic ring current effects in these 20π macrocycles. They display redox properties atypical of parent tetrathia isophlorins. Experimental evidence supports the oxidation of an unstable 19π neutral radical, as a transient intermediate, for the formation of a unique 18π aromatic monocationic species. Spectroscopic and structural characterization revealed the substituent dependent macrocycle oxidation unfamiliar to the chemistry of antiaromatic isophlorinoids.
描述了第一代 S-混乱异佛洛林的合成和氧化还原性质。尽管它们在结构上与混乱卟啉相似，但光谱和计算研究表明，这些 20π大环中存在微弱的反磁环电流效应。它们表现出与母体四硫异佛洛林不同的氧化还原性质。实验证据支持不稳定的 19π中性自由基作为瞬态中间体的形成，用于形成独特的 18π芳香单阳离子物种。光谱和结构表征揭示了取代基依赖性大环氧化，这在反芳香异佛洛林类化合物的化学中是不常见的。
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