title: Efficient, high-yield route to long, functionalized p-phenylene oligomers containing perfluorinated segments, and their cyclodimerizations by zirconocene coupling.
abstract: Linear oligophenylene diynes containing 6, 9, and 12 phenylene rings were synthesized in high yields using the nucleophilic aromatic substitution (S(N)Ar) of perfluoroarenes by aryllithium reagents as the key carbon-carbon bond-forming reaction. This reaction was demonstrated to proceed readily at low temperatures with sterically hindered substrates and in the presence of base-sensitive silylalkynyl groups. Diynes synthesized by this methodology were readily zirconocene-coupled into large dimeric macrocycles using the zirconocene reagent Cp(2)Zr(py)(Me(3)SiC triple bond CSiMe(3)).
authors.affiliation: Center for New Directions in Organic Synthesis, Department of Chemistry, University of California, Berkeley 94720, USA.
authors.forename: J R
authors.initials: JR
authors.lastname: Nitschke
authors.forename: T D
authors.initials: TD
authors.lastname: Tilley