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

作者：Saglam Mehmet F; Fallon Thomas; Paddon Row Michael N^*; Sherburn Michael S^*

来源：Journal of the American Chemical Society, 2016, 138(3): 1022-1032.

DOI：10.1021/jacs.5b11889

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.

• 出版日期2016-1-27