Asymmetric Synthesis of Chiral Cyclopentanes Bearing an All-Carbon Quaternary Stereocenter by Zirconium-Catalyzed Double Carboalumination.

Herein, we report a zirconium-catalyzed enantio- and diastereoselective inter/intramolecular double carboalumination of unactivated 2-substituted 1,5-dienes, which provides efficient and direct access to chiral cyclopentanes through the generation of two stereocenters, including one all-carbon quaternary stereocenter, generally with excellent diastereo- and high enantioselectivity. This tandem carboalumination process creates two new C-C bonds as well as one C-Al bond, which can be oxidized in situ with O or hydrolyzed. Furthermore, the obtained chiral cyclopentanes can be readily functionalized to provide various chiral compounds.

Separation of semiconducting single-walled carbon nanotubes by using a long-alkyl-chain benzenediazonium compound.

We designed and synthesized 4-dodecyloxybenzenediazonium tetrafluoroborate (1), which preferentially reacts with metallic single-walled carbon nanotubes (SWNTs) by kinetic control. We first determined the suitable experimental conditions for the preferential reaction of 1 with individually dissolved SWNTs by monitoring the decrease in absorbance for the metallic SWNT in the range of 400-650 nm in the absorption spectrum of the SWNTs. The reacted SWNTs were thoroughly rinsed with THF to obtain THF-insoluble SWNTs.

Helical superstructures of fullerene peapods and empty single-walled carbon nanotubes formed in water.

Aqueous dispersions of fullerene C70-filled carbon nanotubes (C70@SWNTs or peapods) and empty single-walled carbon nanotubes (empty SWNTs) were prepared with the aid of trimethyl-(2-oxo-2-pyrene-1-yl-ethyl)-ammonium bromide (1), which is a carbon nanotube solubilizer. This is the first report describing the preparation and characterization of the transparent dispersion/dissolution of the peapods. The UV-vis-near-IR spectra of C70@SWNTs-1 and empty SWNTs-1 were almost identical.

Solubilization of single-walled carbon nanotubes by using polycyclic aromatic ammonium amphiphiles in water--strategy for the design of high-performance solubilizers.

We describe the design of polycyclic aromatic compounds with high performance that dissolve single-walled carbon nanotubes (SWNTs). Synthetic amphiphiles trimethyl-(2-oxo-2-phenylethyl)-ammonium bromide (1) and trimethyl-(2-naphthalen-2-yl-2-oxo-ethyl)-ammonium bromide (2) carrying a phenyl or a naphtyl moiety were not able to dissolve/disperse SWNTs in water. By contrast, trimethyl-(2-oxo-2-phenanthren-9-yl-ethyl)-ammonium bromide (3) solubilized SWNTs, although the solubilization ability was lower than that of trimethyl-(2-oxo-2-pyrene-1-yl-ethyl)-ammonium bromide (4) (solubilization behavior observed by using 4 was described briefly in reference 4a).