TY - JOUR
T1 - Discovery and Computational Rationalization of Diminishing Alternation in [n]Dendralenes
AU - Saglam, Mehmet F.
AU - Fallon, Thomas
AU - Paddon-Row, Michael N.
AU - Sherburn, Michael S.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2016/1/27
Y1 - 2016/1/27
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84956797740&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b11889
DO - 10.1021/jacs.5b11889
M3 - Article
SN - 0002-7863
VL - 138
SP - 1022
EP - 1032
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -