Synthesis and properties of corannulene derivatives : journey to materials chemistry and chemical biology

Abstract

Corannulene, also called as [5]-circulene, is a C20H10 fragment of C60. The most interesting property of corannulene is probably bowl structure and bowl-to-bowl inversion. The unique curvature has many for applications in different fields. Today, large-scale synthesis of
corannulene is possible and thus, the time has come to exploit its physical properties.
This dissertation is divided into four areas: 1) efficient synthesis of sympentaarylsubstituedcorannulene 2) solvent effect on the bowl inversion, 3) of the method for solution-phase nanotube synthesis, and 4) designing a
corannulene-based synthetic receptor.
sym-Pentaarylsubstituedcorannulenes are quite attractive compounds because their five-fold symmetry and curvature. The efficient synthesis has been from sym-pentachlorocorannulene with the coupling reaction using Nheterocyclic ligands in a moderately good yield in spite of its five lowreactive The inversion energies of some sym-pentaarylsubstituedcorannulenes have been investigated in different types of solvent. The variable temperature 1H-NMR were measured, and line shape analysis or coalescence approximation were to evaluate the rate parameters. This experiment suggested endo-group interactions of those compounds and shows influences of solvent polarity or volume the inversion energies. In addition, the bowl depths will also be compared and
discussed using the crystallographic structural data.
The high-energy per-ethynylated polynuclear compound decapentynylcorannulene been prepared via aryl-alkyne coupling chemistry of During the reaction, an astonishing compound, 10]annulene was also produced by the corannulene ring-open through the diradical from the enediyne cyclization. The relative structure energetics of those compounds and its carbon nanotube isomer C40H10 are
discussed with some computational data. This study suggests the potential route of first solution-phase single-walled carbon-based nanotubes.
Cholera toxin from Vibrio cholerae and heat-labile enterotoxin from Escherichia coli have similar structures and both belong to the AB5 toxins. The synthetic recepor for those toxins has been synthesized from
sym-pentachlorocorannulene, which has the same five-hold symmetry. The structure a "Finger-Linker-Core" motif and could exploit the pentavalent recognition for toxins. In addition, the synthetic strategy enables the modification of the "Linker" and the introduction of many functional groups.