RESUMO
A series of single-walled carbon nanotube precursors, C3h-symmetric cyclotri(ethynylene)(biphenyl-2,4'-diyl) and cyclotri(ethynylene)(p-terphenyl-2,4â³-diyl), have been prepared by a linear stepwise oligomerization-cyclization route and by statistical intermolecular cyclooligomerization. In addition to producing these members of a novel class of arylene ethynylene macrocycles, 1 and 2, the latter statistical process produces the smaller cyclic dimer, cyclodi(ethynylene)(p-terphenyl-2,4â³-diyl) and the larger cyclic tetramer cyclotetra(ethynylene)(biphenyl-2,4'-diyl). These macrocycles display large Stokes shifts in their fluorescence spectra. Their biphenyl or terphenyl connectivity prevents these macrocycles from achieving full planarity in the ground state, and the ethynylene moieties could provide synthetic access to cyclic arylene oligomers and discrete carbon nanotube segments.
Assuntos
Alcinos/química , Compostos de Bifenilo/síntese química , Compostos Macrocíclicos/síntese química , Compostos de Terfenil/síntese química , Compostos de Bifenilo/química , Fluorescência , Compostos Macrocíclicos/química , Estrutura Molecular , Nanotubos de Carbono/química , Processos Fotoquímicos , Compostos de Terfenil/químicaRESUMO
An intramolecular cyclization cascade reaction has been developed utilizing a high valent palladium intermediate that generates a carbon-carbon and carbon-oxygen bond in a single transformation. This method provides rapid access to highly functionalized tricyclic scaffolds, including spirocyclic cyclohexadienones. Good yields and mild conditions are reported with high tolerance toward oxygen and water.