Separation and on-line concentration of bisphenol A and alkylphenols by micellar electrokinetic chromatography with anionic surfactant

Separation and on-line concentration of bisphenol A and three alkylphenols were investigated by micellar electrokinetic chromatography with the anionic surfactant, sodium dodecyl sulfate. The separation conditions were optimized by the simultaneous addition of the organic solvent and cyclodextrin to the running solution. The separation of hydrophobic analytes and 4-nonylphenol isomers was improved by the addition of 10% methanol and 5 mM beta-cyclodextrin to the running solution. When the sweeping with the running solution was used as the on-line concentration procedure, 69-, 48-, 55- and 41-fold increases in detection sensitivity were obtained for bisphenol A, 4-tert.-butylphenol and 4-(1,1,3,3-tetramethylbutyl)phenol, and the second peak of 4-nonylphenol isomers, respectively. The detection limits were 0.0071, 0.0065, 0.021 and 0.055 mg/l, respectively. These results were better than those with the cationic surfactant, tetradecyltrimethylammonium bromide.     

Thermal decomposition of acrylamide from polyacrylamide

Ion-attachment mass spectrometry with a temperature-programed direct probe allows the detection of intact pyrolysis products. It, therefore, offers the opportunity to monitor directly thermal byproducts on a real-time basis and potentially to detect thermally unstable products. With this technique, we investigated the thermal decomposition of polyacrylamide (PAA). Pyrolysis of PAA at around 450?°C produces many products (e.g., amides, imides, nitriles, ketones, aldehydes, and acrylamide oligomers). Acrylamide, which is a possible carcinogen, is produced abundantly in various industries, and, therefore, continues to be a cause for concern. We also investigated the kinetics of the thermal decomposition of PAA, and observed that the degradation of acrylamide obeys Arrhenius kinetics, which allowed us to correlate the rate constant with the absolute temperature and the activation energy. The activation energy of thermal decomposition was calculated from selected ion-monitoring curves of acrylamide.     

Reaction of acylsilanes with α-sulfinyl carbanions: regioselective synthesis of silyl enol ethers

The reaction of acylsilanes with α-sulfinyl carbanions such as α-lithioalkyl sulfoxide is described. The reaction proceeds to give silyl enol ethers preferentially through the initial formation of the α-silyl alkoxide intermediates. In particular, the products derived from enolizable acylsilanes were the regio-defined silyl enol ethers that cannot be obtained by usual enolization of the corresponding unsymmetrical ketones with base.     

Construction of Robust Ruthenium(salen)(CO) Complexes and Asymmetric Aziridination with Nitrene Precursors in the Form of Azide Compounds That Bear Easily Removable N‐Sulfonyl Groups

We synthesized new Ru(salen)(CO) complexes of high durability and achieved aziridination with good to excellent enantioselectivity by using azide compounds that contain an easily removable N‐sulfonyl group, such as the 2‐(trimethylsilyl)ethanesulfonyl group, as a nitrene precursor. Aziridination of less‐reactive α,β‐unsaturated esters (and amides) proceeded with excellent enantioselectivities, from which it is inferred that an electrophilic species is the active species of this reaction. The present asymmetric aziridination provides a useful tool for introducing optically active nonprotected amine groups.     

Total Synthesis,Stereochemical Revision,and Biological Assessment of Iriomoteolide-2a

Iriomoteolide-2a is a marine macrolide metabolite isolated from a cultured broth of the benthic dinoflagellate Amphidinium sp. HYA024 strain. This naturally occurring substance was reported to show remarkable cytotoxic activity against human cancer cell lines HeLa and DG-75 and in vivo antitumor activity against murine leukemia P388 cell line. Herein, the total synthesis, stereochemical revision, and biological assessment of iriomoteolide-2a are reported in detail. Total synthesis of the proposed structure 1 of iriomoteolide-2a featured a late-stage convergent assembly of three components by a Suzuki–Miyaura coupling, an esterification, and a ring-closing metathesis. However, the NMR data of synthetic 1 were not identical to those of the natural product. Careful analysis of the NMR data of the authentic material and synthesis/NMR analysis of appropriately designed model compounds led to consideration of four possible stereoisomers 2 – 5 as candidates for the correct structure. Accordingly, total syntheses of 2 – 5 were achieved by taking advantage of the convergent strategy, and comparison of the NMR spectra of synthetic 2 – 5 with those of the natural product led to the conclusion that 5 shows the correct relative configuration of iriomoteolide-2a. The absolute configuration of this natural product was finally established through chiral HPLC analysis of synthetic 5 /ent- 5 with the authentic sample. The antiproliferative activity of the synthetic compounds was assessed against HeLa and A549 cells to show that, in contrast to expectation, synthetic 5 and ent- 5 were only marginally active in these cell lines. This work clearly underscores the vital role of total synthesis in the establishment of the structure and biological activity of natural products.