Conformationally controlled (entropy effects), stereoselective vibrational quenching of singlet oxygen in the oxidative cleavage of oxazolidinone-functionalized enecarbamates through solvent and temperature variations

On photooxygenation (methylene blue as sensitizer) of E/Z enecarbamates, equipped with the oxazolidinone chiral auxiliary, the oxidative cleavage of the alkenyl functionality releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense (R vs S) of the stereoselectivity in the MDB formation depends on the choice of the alkene configuration; the efficacy of stereocontrol may be tuned by appropriate solvent and temperature conditions. Highlighted is the finding that the formation of the preferred MDB enantiomer (R or S) depends for the E isomer on the chosen solvent and temperature, but not for the corresponding Z isomer. The activation parameters for the various solvents disclose that differential entropy effects (ΔΔS^‡) dominate the conformationally more flexible E diastereomers. As mechanistic rationale for this unprecedented conformationally imposed stereochemical behavior, we propose the competitive action of stereoselective vibrational quenching of the attacking singlet oxygen by the enecarbamate versus sterically controlled stereoselective oxidative cleavage of its double bond.     

Molecular Recognition Study on a Supramolecular System. Part 21. Inclusion Complexation Thermodynamics of Aliphatic Alcohols by Organoselenium Modified β-Cyclodextrins

The spectrophotometric titrations have beenperformed at 25–40 °C in aqueous solution to give the complexstability constants and the thermodynamic parametersfor the stoichiometric 1 : 1 inclusion complexation ofvarious aliphatic alcohols withmono[6-(phenylseleno)-6-deoxy]--cyclodextrin (2),mono[6-(o-, m-,p-tolylseleno)-6-deoxy]--cyclodextrin (3–5),mono[6-(p-chloro-phenyl-seleno)-6-deoxy]--cyclodextrin(6), mono[6-(benzylseleno)-6-deoxy]--cyclodextrin (7) and mono[6-(naphthaleneseleno)-6-deoxy]--cyclodextrin(8). On thebasis of the present and previous results, themolecular binding abilities and selectivities forguest aliphatic alcohols of the host -cyclodextrinderivatives (2–8) are discussed comparatively and globallyfrom the thermodynamic point of view. Thethermodynamic parameters obtained are criticalfunctions of the size/shape of aliphatic alcohols, andthe position and type of the substituent introduced tothe aromatic ring of -cyclodextrin's sidearm,which are elucidatedin terms of the conformational, electrostatic,hydrogen-bonding, and hydrophobic effects.     

Alternating copolymerization of polar vinyl monomers in the presence of zinc chloride. I. Propagation and initiation of the copolymerization of acrylonitrile with styrene copolymer

Copolymerization of acrylonitrile with styrene spontaneously occurred on addition of zinc chloride without addition of any other radical initiator. The composition of the copolymer approached that of strictly alternating copolymer as zinc chloride added to the copolymerization system increased. The significance of the apparent monomer reactivity ratios of this copolymerization system was studied from a kinetic point of view, and it was shown that the monomer sequence distribution is indicated by the apparent monomer reactivity ratios. Further, equations which represent the relation between the apparent monomer reactivity ratios and Q,e values at a given salt concentration were derived. These equations reasonably accounted for the decrease of the apparent monomer reactivity ratios of the copolymerization of acrylonitrile with styrene in the presence of zinc chloride and the behavior of the other acrylonitrile copolymerization systems in the presence of zinc chloride. The initiation step of the spontaneous radical copolymerization of acrylonitrile with styrene in the presence of zinc chloride was explained by a cross-initiation mechanism.     

Studies directed towards the asymmetric total synthesis of antileukemic lignan lactones. Synthesis of optically pure key intermediate and its utility

By the self-immolative asymmetric synthesis, optically pure key intermediate β-piperonyl-γ-lactone (R)-(+)-$\text{6}$ was found to be prepared in reasonable yield from the easily available chiral γ-lactone synthon ($\text{1}$) which had been also reported to give an antipode (S)-(-)-$\text{6}$. The optically pure (R)-(+)-$\text{6}$ was shown to be converted successfully into several optically pure natural lignan lactones.     

Synthesis of new azonia-helicenes with a quaternary nitrogen at the inner helix skeleton

The 16c-azonia[6]helicene salts, in which a carbon atom at the inner helix skeleton of [6]helicene is replaced by a quaternary nitrogen atom, have been synthesized by photo-induced intramolecular quater-nization of 2-[2-(1-chloronaphthyl)vinyl]benzo[h]quinolines in acetonitrile.     

Liquid chromatographic-mass spectrometric analysis for screening of patients with cystinuria, and identification of cystine stone.

Analyses of amino acids in the urine of a normal human and of patients with heterozygous and homozygous cystinuria have been carried out, using liquid chromatography-mass spectrometry with an atmospheric pressure ionization interface system. A kidney cystine stone was also analysed by this system. Very intense quasi-molecular ions ([M + H]+) of standard cystine, arginine, lysine and ornithine were observed on mass chromatograms as base peaks. Mass chromatograms of the urine samples from a normal human and from patients with heterozygous and homozygous cystinuria were easily distinguishable. The retention times in the mass chromatogram and mass spectrum of kidney stone cystine was almost the same as that of authentic cystine.     

Determination of Low-Level Ethylenediaminetetraacetic Acid in Water Samples by Ion Chromatography with Ultraviolet Detection

A convenient and sensitive ion chromatographic (IC) method for the analysis of ethylenediaminetetraacetic acid (EDTA) in water samples was proposed. Using a fast reversible reaction of free EDTA and metal–EDTA complexes into Fe(III)–EDTA complex in the presence of Fe(III) ions, sample solutions were applied to an ion-exchange column using a mobile phase (pH 2.3), which was composed of 100 μM Fe(III) chloride and 5 mM methanesulfonic acid. The addition of Fe(III) solution (100 μL) containing 10 mM Fe(III) chloride and 0.5 M methanesulfonic acid to the sample solution (10 mL) permitted the injection of a large volume (400 μL) of sample, which allowed for greater sensitivity. The proposed IC method gave a highly linear (r ² > 0.999) calibration curve ranging 0.005–1.0 μM EDTA and had a limit of detection of 1.5 nM. High repeatability (RSD < 2.1%) and recoveries (88–108%) were also obtained. With this method, total EDTA level in raw and drinking waters were analyzed successfully.     

Improved separation of alpha chains of collagen type I, type III, and type V by noninterrupted electrophoresis using thioglycolic acid as a negatively charged reducer

Improved separation of alpha chains of collagen type I (alpha 1 [I]2 alpha 2[I]), type III(alpha 1[III]3), and type V (alpha 1[V]alpha 3[V])was achieved by noninterrupted sodium dodecyl sulfate-polyacrylamide gel electrophoresis with a negatively charged reducer, thioglycolic acid. The thioglycolic acid, added to the running buffer of the cathodic reservoir, in the middle of electrophoresis quickly migrated in the gel anode, reducing interchain disulfide linkages in collagen type III and dissociating it into its alpha chain monomer, alpha 1[III], without an interruption of electrophoresis. The alpha chain, alpha 1[III], migrated more slowly than the alpha 1 [I] and alpha 2[I] chains of collagen type I, resulting in an excellent separation of alpha 1[III] from alpha 1[I]. The mobility of alpha 1[III] could be controlled by varying the time of thioglycolic acid addition to the running buffer. This enabled us not only to separate alpha 1[III] from alpha 1[I] and alpha 1[V], but also to precisely quantitate these alpha chains, even at low protein loading of mixed samples.     

Convergent syntheses of polycyclic ethers. Illustrations of the utility of acetal-linked intermediates

One of the most characteristic and spectacular class of compounds isolated from marine sources is the polycyclic ethers. Following the initial report of the structural determination of brevetoxin B, a variety of novel polycyclic ethers have begun to surface. These natural products include ciguatoxins, gambierol, gambieric acids, yessotoxins and gymnocins, each of which exhibit distinct biological properties such as cytotoxicity and neurotoxicity, as well as antiviral and antifungal activities. Because of these intriguing biological activities and their complex molecular architecture, the total synthesis of these compounds has been pursued by many laboratories over two decades. In particular, the development of novel convergent strategies to assemble the structural fragments is crucial for the successful construction of these nano-scale molecules. This Perspective will focus on a recent convergent methodology using an acetal-linkage as a key motif. Application of this methodology culminated in the total syntheses of gambierol and ciguatoxin CTX3C.     

Electron spin resonance study of polymerization of butadiene with tris(acetylacetonato)titanium and triethylaluminum

ESR spectra of homogeneous catalyst derived from tris(acetylacetonato)titanium(III) and triethylaluminum were observed at several temperatures from ?78°C, to +25°C, at molar ratios of aluminum to titanium of 1–108. At ?78°C, this catalyst yields a violet complex which shows an ESR signal with a g value of 1.959 and is associated with the first intermediate. At ?40°C to ?30°C, this signal decreases, and two signals with g values of 1.947 and 1.960 are observed. The latter two signals diminish at ?5°C to +10°C, while two kinds of new signals with g values of 1.965 and 1.969 appear overlapping each other. The structures of the species corresponding to these five signals are discussed on the basis of the ESR spectra, the intensity change, and the unpaired spin distribution. A new signal with a g value of 1.978 is found in the presence of butadiene at 25°C at Al/Ti > 8 and is assigned to a growing end of polybutadiene with this catalyst. The polymer yield increases remarkedly at Al/Ti molar ratios greater than 10. The microstructure of the resulting polymer consists almost completely of 1,2 units. The structure of the growing end is proposed to be a titanium (III) species containing two 1-substituted allyl groups, by comparison with the structure ascribed to the growing end of polybutadiene with n-butyl titanate-triethylaluminum catalyst.