Discovery and Computational Rationalization of Diminishing Alternation in [n]Dendralenes

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• 作者：Mehmet F. Saglam ; Thomas Fallon ; Michael N. Paddon-Row ; Michael S. Sherburn
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：January 27, 2016
• 年：2016
• 卷：138
• 期：3
• 页码：1022-1032
• 全文大小：777K
• ISSN：1520-5126

文摘

The [n]dendralenes are a family of acyclic hydrocarbons which, by virtue of their ability to rapidly generate structural complexity, have attracted significant recent synthetic attention. [3]Dendralene through [8]dendralene have been previously prepared but no higher member of the family has been reported to date. Here, we describe the first chemical syntheses of the “higher” dendralenes, [9]dendralene through [12]dendralene. We also report a detailed investigation into the spectroscopic properties and chemical reactivity of the complete family of fundamental hydrocarbons, [3]dendralene to [12]dendralene. These studies reveal the first case of diminishing alternation in behavior in a series of related structures. We also report a comprehensive series of computational studies, which trace this dampening oscillatory effect in both spectroscopic measurements and chemical reactivity to conformational preferences.