Broad-spectrum radical cyclizations boosted by polarity matching. Carbonylative access to alpha-stannylmethylene lactams from azaenynes and CO

Free-radical mediated stannylcarbonylation of azaenynes provides a general [n + 1]-type annulation approach leading to alpha-stannylmethylene lactams. The cyclization is unusual in its breadth, covering 4-exo, 5-exo, 6-exo, 7-exo, and 8-exo modes.     

Photoreactions of β-aziridinylacrylonitriles and acrylates with alkenes: formation of head-to-head adducts and application to the preparation of pyrrolizidine alkaloid

The photochemical C,C-bond cleavage of N-benzyl β-aziridinylacrylonitrile 1 and acrylate 2 and the subsequent [3+2] cycloaddition with electron-deficient alkenes afforded head-to-head adducts selectively and efficiently. Irradiation of N-phenyl aziridine 3 with acrylonitrile gave adducts, but photoreaction of N-benzoyl aziridine 4 and thermal reactions of 3 and 4 with alkenes yielded C(γ),N-cleaved products instead of cycloadducts. N-trityl aziridine 5 also reacted with electron-deficient alkenes, affording 2,3-cis-pyrrolidine derivatives exclusively. A formal synthesis of a pyrrolizidine alkaloid, isoretronecanol (27), starting from 5 was achieved in a convenient manner.     

An anionic strategy for three- and four-component coupling reactions leading to ketone frameworks based on vinylogous conversion of dilithio ketone alpha,beta-dianions

[reaction: see text] Ketone alpha,delta-dianions are generated by vinylogous extension of ketone alpha,beta-dianions with alkenes such as vinylarenes, vinylsilanes, and vinyl sulfides, which then undergo reactions at the delta and alpha positions with different electrophiles, creating ketone frameworks. This work represents a cascade-type anion method that achieved three- and four-carbon component assembly reactions leading to ketones.     

Superconductor-insulator transition in a two-dimensional array of resistively shunted small josephson junctions

Using a scattering technique based on a parametrized linear combination of atomic orbitals Hamiltonian, we calculate the ballistic quantum conductance of multiwall carbon nanotubes. We find that interwall interactions not only block some of the quantum conductance channels, but also redistribute the current nonuniformly over individual tubes across the structure. Our results provide a natural explanation for the unexpected integer and noninteger conductance values reported for multiwall nanotubes by Stefan Frank et al. [Stefan Frank et al., Science 280, 1744 (1998)].     

Ion-extraction by a crown ether with a photoresponsive carboxylate cap.

A new photoresponsive crown ether (I) with an azobenzene-4-oxyacetate function was synthesized. The photo-isomerized cis-(1) extracted K⁺ ion more selectively than trans-(I) and the thermal cis-trans isomerization was suppressed by added metal ions.     

Redox-switched crown ethers monocrown-biscrown interconversion coupled with redox of a thiol-disulfide couple

To give a redox-switch function to crown ethers, 4′-mercaptomono-benzo-15-crown-5 (CrSH) and its oxidized disulfide form (CrSSCr) were synthesized. The solvent extraction proved that the ion affinity of CrSH is generally greater than that of CrSSCr.     

A copper-free Sonogashira coupling reaction in ionic liquids and its application to a microflow system for efficient catalyst recycling

[reaction: see text] The PdCl2(PPh3)2-catalyzed Sonogashira coupling reaction, in good to high yields, was performed in an ionic liquid ([BMIm][PF6]) in the absence of a copper salt. The use of an ionic liquid allows for the facile separation and recycling of the catalyst. The application of the above reaction in a microflow system in conjunction with an IMM micromixer was also successful.     

Flow Friedel–Crafts alkylation of 1-adamantanol with arenes using HO-SAS as an immobilized acid catalyst

In this communication flow Friedel–Crafts alkylation was studied using hydroxy-substituted sulfonic acid-functionalized silica as a catalyst and 1-adamantanol as a model substrate. The reaction of 1-adamantanol ( 1a ) with toluene ( 2a ) proceeded well with 5 min of residence time at 120°C to give good yield of 1-tolyladamantane ( 3a ) as a 1:9 mixture of meta and para isomers. When the flow synthesis was carried out over 2.5 hr of running time, the collected five fractions contain the product 3a in 97–92% yields, suggesting the durability of the catalyst.     

A rosette cooling cell: More effective container for solubilization of single-walled carbon nanotubes under probe-type ultrasonic irradiation

Probe-type ultrasonication has been employed for surfactant-aided solubilization, or individualization, of single-walled carbon nanotubes (SWNTs). The resulting solution can be used not only for spectroscopic analyses such as absorption, photoluminescence, and circular dichroism, but also for separation by density gradient ultracentrifugation, dielectrophoresis, chromatography, and polymer wrapping. In spite of its importance, the sonochemical processing of SWNTs has not been considered seriously. Herein, we report on a more efficient cooling cell for probe-type ultrasonication. As compared with a conventional cylindrical cell, the concentration of the SWNTs solubilized in water was found to be almost double in a rosette cooling cell after ultracentrifugation. The efficiency of a rosette cell can be attributed to the higher efficiency in circulation and cooling of the SWNT dispersion as well as enhancement of the cavitation process.     

Bis(tert‐butylpyrene) Nanotweezers and Nanocalipers: Enhanced Extraction and Recognition Abilities for Single‐Walled Carbon Nanotubes

We developed a host–guest methodology for separation of single‐walled carbon nanotubes (SWNTs) according to the handedness, diameter and metallicity by the use of diporphyrin nanotweezers and nanocalipers. Although the pyrene has been frequently used to replace porphyrin, due to a similar affinity to the surface of SWNTs and better availability, the extraction and recognition abilities of dipyrene nanotweezers were not so good as those of diporphyrin ones as we reported previously. However, introduction of a tert‐butyl substituent at the 7′‐position of 2‐pyrene is found to enhance the extraction and recognition abilities of dipyrene nanotweezers and nanocalipers. That is, (6,5)‐SWNTs were obtained in high purity by use of bis(tert‐butylpyrene) nanotweezers with a phenanthrene spacer and metallic SWNTs were highly enriched by use of bis(tert‐butylpyrene) nanocalipers with a carbazole–anthracene–carbazole spacer.