Quantcast

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

Research paper by Mehmet F. Saglam, Thomas Fallon, Michael N. Paddon-Row, Michael S. Sherburn

Indexed on: 15 Jan '16Published on: 31 Dec '15Published in: Journal of the American Chemical Society



Abstract

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.

Figure jacs.5b11889.2.jpg
Figure jacs.5b11889.3.jpg
Figure jacs.5b11889.4.jpg
Figure jacs.5b11889.5.jpg
Figure jacs.5b11889.6.jpg
Figure jacs.5b11889.7.jpg
Figure jacs.5b11889.8.jpg
Figure jacs.5b11889.9.jpg
Figure jacs.5b11889.10.jpg
Figure jacs.5b11889.11.jpg
Figure jacs.5b11889.12.jpg
Figure jacs.5b11889.13.jpg
Figure jacs.5b11889.14.jpg
Figure jacs.5b11889.15.jpg
Figure jacs.5b11889.16.jpg
Figure jacs.5b11889.17.jpg
Figure jacs.5b11889.18.jpg
Figure jacs.5b11889.19.jpg
Figure jacs.5b11889.20.jpg