title: Discovery and Computational Rationalization of Diminishing Alternation in [n]Dendralenes.
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.
authors.affiliation: Research School of Chemistry, Australian National University , Canberra, Australian Capital Territory 2601, Australia.
authors.forename: Mehmet F
authors.initials: MF
authors.lastname: Saglam
authors.affiliation: Research School of Chemistry, Australian National University , Canberra, Australian Capital Territory 2601, Australia.
authors.forename: Thomas
authors.initials: T
authors.lastname: Fallon
authors.affiliation: School of Chemistry, The University of New South Wales , Sydney, New South Wales 2052, Australia.
authors.forename: Michael N
authors.initials: MN
authors.lastname: Paddon-Row
authors.affiliation: Research School of Chemistry, Australian National University , Canberra, Australian Capital Territory 2601, Australia.
authors.forename: Michael S
authors.initials: MS
authors.lastname: Sherburn
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D061565:Cycloaddition Reaction; D008968:Molecular Conformation
chemical_list: C527474:3,4,5-trimethylenehepta-1,6-diene; D000475:Alkenes