Conclusive evidence of the trapping of primary ozonides

[reaction: see text] Anomalous ozonolysis of strained bicyclic allylic alcohols yields alpha-hydroxymethyl ketones. The proposed mechanism involves an unusual trapping of the primary ozonide that undergoes a Grob-like fragmentation instead of dissociating into the Criegee intermediates.     

Electron paramagnetic resonance study of partially oriented clay platelets intercalated with copper(II) 1,4,8,11-tetraazacyclotetradecane

Electron paramagnetic resonance (EPR) spectra of powder and oriented films of montmorillonite, hectorite, and saponite intercalated with [Cu(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) exhibit three components: an orientation-dependent component without hyperfine features, an orientation-dependent component with hyperfine features, and an orientation-independent component without hyperfine feature. EPR spectra of [Cu(cyclam)](2+)-saponite, which exhibit only two components and the best resolved hyperfine features, were simulated. The spectra indicate that a large portion of the saponite platelets are inclined to the glass surface, although they tend to align with their basal planes parallel to the glass surface. The orientation-dependent spectra could be simulated by introducing a Gaussian distribution with a standard deviation of 20 degrees for the inclination angle. The standard deviation may be used as a disorder parameter for the microcrystals assembled on glass plates. Spectral simulation also shows that the CuN(4) plane of [Cu(cyclam)](2+) is parallel to the clay layers. EPR spectra of some other partially oriented systems are also discussed.     

Über sechsgliedrige Heterocyclen mit Phosphor-, Stickstoff- und Schwefelatomen im Ring

Cyclic sulphurylphosphazochloride (I: formula see ?Inhaltsübersicht”?) reacts with ammonia or methylamine forming the. tetramide(II) and (III), respectively, and with aniline or dimethylamine forming the diamide (IV) resp. (V). The synthesis of the diphenyl derivative (VI) is achieved starting from C₆H₅? PCl₄. (II) gives with PCl₅ the ionic compound (VII).     

Synthesis of 4-acetylisocoumarin: first total syntheses of AGI-7 and sescandelin

A practical synthetic route to 4-acetylisocoumarins and the first total synthesis of AGI-7 (5) and sescandelin (4) are described. The readily available homophthalate 8 was transformed to the vinylogous amide ester 13 in high overall yield. Upon treatment of 13 with refluxing aqueous formic acid, the desired 4-acetylisocoumarin (5) and its regioisomer 3-methyl-4-formylisocoumarin (17) were produced in a 3:1 ratio. After separation of the desired product (5) from the unwanted minor isomer, the enantioselective reduction of AGI-7 by borane in the presence of Corey's (S)-oxazaborolidine reagent afforded (+)-sescandelin (4) with a 93% ee.     

Synthesis of four diastereomeric 3,5-dialkoxy-2,4-dimethylalkanals by a simple extension of the non-aldol aldol process to bis(propionates)

[formula: see text] The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4-dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base.     

Surface-initiated growth of poly d(A-T) by Taq DNA polymerase

In this paper, we report surface-initiated d(A-T) polymerization by Taq DNA polymerase as a method for constructing DNA-tethered surfaces using an enzyme. The enzymatic polymerization was conducted successfully via two steps: tethering of oligo d(A-T)s onto the surface presenting carboxylic acids by amide coupling and surface-initiated polymerization using Taq DNA polymerase. In this enzymatic polymerization process, the design and construction of carboxylic acid-presenting surfaces were found to be an important factor: DNA growth did not occur on the gold surface coated only with the self-assembled monolayer (SAM) of 16-mercaptohexadecanoic acid (MHDA), but effectively proceeded on the surfaces presenting mixed SAMs of MHDA and 1-pentadecanethiol. The coupling of oligo d(A-T)s and the subsequent DNA polymerization reaction were characterized by polarized infrared external reflectance spectroscopy, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy.     

Self-assembling structures of long-chain phenyl glucoside influenced by the introduction of double bonds

Four long-chain phenyl glucoside amphiphiles possessing a saturated or unsaturated long alkyl chain group as the self-assembling unit of a highly organized molecular architecture were synthesized. Their self-assembling properties were investigated by EF-TEM, SEM, CD, FT-IR, and XRD. Compound 2 possessing one double bond in the lipophilic portion showed twisted helical fibers, which formed a bilayered structure with a 3.59 nm period, while compound 3 showed the helical ribbons and left-handed nanotubular structures with 150-200 nm inner diameters and ca. 20 nm of wall. Very interestingly, compound 4 possessing three double bonds showed a nanotubular structure with ca. 70 nm of inner diameter through a helical ribbon, which formed a loose bilayered structure with 4.62 nm. These results indicate that self-assembling properties strongly depend on the number of cis double bonds.