Highly enhanced enantioselectivity in the memory of chirality via acyliminium ions

[reaction: see text] Electrochemical oxidation of N-acylated serine derivative 1b in methanol gave optically active methoxylated compound 2b with an enantiomeric excess of up to 80%. The bulky o-phenyl benzoyl N-protecting group was found to be the main contributing factor for the enhanced enantioselectivity. The mechanistic aspect of this methoxylation reaction was investigated and found to proceed via a retention mechanism.     

Radical polymerization behavior of N-vinylsaccharin

Synthesis and radical polymerization behavior of N-vinylsaccharin (1) are described. Radical homopolymerization of 1 was carried out in the presence of a radical initiator for 24 h to afford the polymer containing a saccharin moiety in the side group, which was insoluble in common organic solvents. Among the copolymers of 1 with various vinyl monomers such as vinyl acetate (VAc), methyl acrylate (MA), acrylonitrile (AN), and styrene (St), only the copolymer [copoly(1-St)] obtained from 1 and St was soluble in common organic solvents. In the copolymerization of 1 and St, the Q and e values of 1 were estimated to be 0.10 and −1.60, respectively. These values are similar to those of N-vinylphthalimide (Q = 0.36, e = −1.52). The reaction of copoly(1-St) with LiAlH₄ was carried out in THF for 24 h to convert the saccharin moiety into the ring-opened structure bearing hydroxy and sulfonamide groups. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3419–3426, 1999     

Solubilization of endocrine disruptors in micellar media

The interaction of endocrine disruptor chemicals (EDCs) such as nonylphenol (NP) and β-estradiol with cationic micelle of hexadecyltrimethylammonium ion (HTA⁺) and a monolayer of HTA⁺ ion adsorbed at the electrode surface has been investigated in the presence of hydrophilic modified (2-hydroxypropyl)-β-cyclodextrin. NP, which has a similar structure to HTA⁺, decreased the critical micelle concentration (cmc) of hexadecyltrimethylammonium bromide more effectively. At the low HTA⁺ concentration, HTA⁺ inhibited the adsorption of I₂. However, as the HTA⁺ concentration increased, a monolayer of HTA⁺ was formed at the electrode surface and caused the adsorption of iodine molecule (I₂). In the presence of micelle, the I₂ was dissolved in the micelle. Both EDCs caused the formation of HTA⁺ monolayer even at the HTA⁺ concentration below the cmc.     

A facile synthesis of 9-dialkylamino-9H-pyrrolo[1,2-a]indoles via iminium salts generated from 2-(pyrrol-1-yl)benzaldehydes and secondary amine hydrochlorides in the presence of NaI/TMSCl/Et3N

The NaI/TMSCl/Et₃N-mediated condensation between 2-(pyrrol-1-yl)benzaldehydes and secondary amine hydrochlorides followed by intramolecular trapping of the resulting iminium carbon by the 2-position of the pyrrole ring afforded corresponding 9-dialkylamino-9H-pyrrolo[1,2-a]indoles generally in good yields.     

An ab initio MO study of allene episulfide, cyclopropanethione and thioxyallyl

The electronic structures of allene episulfide, cyclopropanethione and thioxyallyl were examined by ab initio MO calculations and were compared with those of the corresponding oxygen compounds, allene oxide, cyclopropanone and oxyallyl. The difference in reactivities of allene episulfide and allene oxide was also speculatively estimated from the calculated electronic structures. The lowest singlet state of thioxyallyl was predicted to be the B₂ state, which corresponds to the σ, π-diradical. A small activation energy is required for the cyclization of the B₂ state to give allene episulfide. The A₁ singlet state lies 11 kcal mol⁻¹ higher than the B₂ singlet state and undergoes the disrotatory rotation of methylene groups to give cyclopropanethione with no activation energy.     

Numerical study of self-sustained oblique detonation in a non-uniform mixture

Self-sustained oblique detonation behind a spherical projectile formed in a non-uniform H₂/O₂/Ar mixture was numerically investigated. A hypersonic combustible mixture flow around a 4.76 mm diameter body was modeled to be flowing at 2500 m/s and 100 kPa. The concentration gradient was prescribed applying the Gaussian distribution to hydrogen concentration. Axisymmetric Euler equations including a detailed kinetics of 9 species and 27 elementary reactions were solved with an explicit 2nd-order time integration scheme combined with point implicit method for chemical reaction. Oblique detonation was always obtained when the mixture on the centerline was stoichiometric, as it is for a uniform mixture, and a broader range of equivalence ratio could sustain oblique detonation far from the sphere. Local detonation angle was revealed to reasonably match Chapman-Jouguet analytical solutions with a minor difference attributed to curvature, less reactive composition, and the concentration gradient. Also, a strongly fuel-rich region encountered decoupling of the shock-flame, in which an abrupt deflection of the shock front appeared. These decoupling phenomena can be attributed to a slower kinetics of a less reactive mixture. All of interesting findings in this study will also benefit understanding of various form of detonation in non-uniform mixture taking advantage of the analogy between them.     

Low radiation loss Y-junctions in planar dielectric optical waveguides

A simple structure is proposed to reduce radiation losses of Y-junctions in planar optical waveguides by decreasing refractive indices near the branching regions. The losses of the properly designed Y-junctions can be reduced by around an order of magnitude compared with those of conventional ones when the branching angles are large.     

Photo-oxygenations of 1H-azepine derivatives isolation and characterization of the [6+2] cycloaddition product

The reactions of 1H-azepine derivatives ($\text{1a-b}$ and $\text{4}$) with singlet oxygen gave the [6+2] cycloadducts ($\text{2a-b}$) and the [4+2] cycloadducts ($\text{3a-b}$ and $\text{5}$). The thermal and base-catalyzed rearrangements of the oxygen-adducts were investigated.