Dimethylsilyl ketene acetal as a nucleophile in asymmetric Michael reaction: enhanced enantioselectivity in oxazaborolidinone-catalyzed reaction

[reaction: see text] Dimethylsilanyl [Me2Si(H)] ketene S,O-acetal 6b is an effective nucleophile that retards the undesirable Si+-catalyzed racemic pathway in the oxazaborolidinone-catalyzed asymmetric Michael reaction. Through the further suppression of the Si+-catalyzed pathway by carrying out the reaction in the presence of 2,6-diisopropylphenol and t-BuOMe as additives, enantioselectivity up to 98% ee could be achieved for a variety of acyclic enones.     

Signals for scalar top quark atep collider HERA

In the framework of the minimal supersymmetric standard model (MSSM) and theR-parity breaking model (RBM), we investigate production processes of the scalar top (stop) at HERA energies. These models are characterized by the possible existence of the light stop whose mass is lighter than those of the top quark and the other squarks. It is shown that in the MSSM the stop pair production via boson-gluon fusion gives a sizeable cross section and the most serious background $ep \to ec\bar cX$ could be suppressed by appropriate kinematical cuts. We also show that in the RBM the stop is singly produced in the neutral current processes and we have a clear signal as a sharp peak in the Bjorken parameterx distribution of the scattered electron.     

Inhibitory effects of tetragalloylglucose on the complex II of mitochondrial respiratory chain of Ascaris muscle

The effects of tetragalloylglucose (1,2,3,6-tetra-O-galloyl-beta-D-glucose) on purified complex II (succinate-ubiquinone oxidoreductase) of the mitochondrial electron transport system of Ascaris muscle were studied. Both succinate-ubiquinone-1 (Q1) oxidoreductase, and succinate dehydrogenase measured with 3-(4,5-dimethylthiazol-2-yl)- 2,5-diphenyltetrazolium bromide (MTT) in the presence of phenazine methosulfate (PMS) were inhibited by tetragalloylglucose. The inhibitions of both reductase activities of complex II were of competitive type, and the inhibitor constant (Ki) for Ascaris complex II (148 nM) was lower than that for rat liver complex II (1.5 microM). Thus, Ascaris complex II is much more sensitive to this inhibitor than the mammalian counterpart.     

Synthesis of alanine and leucine by reductive amination of 2-oxoic acid with combination of hydrogenase and dehydrogenase

Alanine synthesis by reductive amination of pyruvate was performed by the combination of NADH regeneration system and alanine dehydrogenase (AlaDH). The conversion of pyruvate to alanine was 99% after 1 h. Leucine synthesis was also carried out by the combination of NADH regeneration system and leucine dehydrogenase (LeuDH). The conversion of 4-methyl-2-oxovalerate to leucine was 60% after 1.5 h.     

Radiation-induced addition reaction of carbon tetrachloride onto 1,2-polybutadiene

The γ-ray-induced addition reaction of carbon tetrachloride onto syndiotactic 1,2-polybutadiene film and liquid 1,2-polybutadiene was carried out at room temperature. In the film gelation was pronounced and the rate of addition increased as the crystallinity of the polymer decreased. In the liquid gelation, which makes the polymer insoluble in carbon tetrachloride, did not take place, although a definite crosslinking reaction was noticed. In this case the appearance of the product changed from a viscous liquid to a white powder as the reaction proceeded. Its structure was compared with that of chlorinated 1,2-polybutadiene. The addition of carbon tetrachloride to the vinyl group in liquid 1,2-polybutadiene caused an anti-Markownikoff-type reaction and was accompanied by an unexpectedly large vinyl depletion in the polymer. The total decrease in the vinyl group was found to be much larger than that brought about by the addition of carbon tetrachloride. This discrepancy was attributed to a cyclization and crosslinking reaction ascribed to the vinyl group bound by the main chain. Cyclization and crosslinking were less noticeable in the chlorination than in the carbon tetrachloride.     

m-Diethynylbenzene macrocycles: syntheses and self-association behavior in solution

m-Diethynylbenzene macrocycles (DBMs), buta-1,3-diyne-bridged [4(n)]metacyclophanes, have been synthesized and their self-association behaviors in solution were investigated. Cyclic tetramers, hexamers, and octamers of DBMs having exo-annular octyl, hexadecyl, and 3,6,9-trioxadecyl ester groups were prepared by intermolecular oxidative coupling of dimer units or intramolecular cyclization of the corresponding open-chain oligomers. The aggregation properties were investigated by two methods, the (1)H NMR spectra and the vapor pressure osmometry (VPO). Although some discrepancies were observed between the association constants obtained from the two methods, the qualitative view was consistent with each other. The analysis of self-aggregation by VPO revealed unique aggregation behavior of DBMs in acetone and toluene, which was not elucidated by the NMR method. Namely, the association constants for infinite association are several times larger than the dimerization constant, suggesting that the aggregation is enhanced by the formation of dimers (a nucleation mechanism). In polar solvents, DBMs aggregate more strongly than in chloroform due to the solvophobic interactions between the macrocyclic framework and the solvents. Moreover, DBMs self-associate in aromatic solvents such as toluene and o-xylene more readily than in chloroform. In particular, the hexameric DBM having a large macrocyclic cavity exhibits extremely large association constants in aromatic solvents. By comparing the aggregation properties of DBMs with the corresponding acyclic oligomers, the effect of the macrocyclic structure on the aggregation propensity was clarified. Finally, it turned out that DBMs tend to aggregate more readily than the corresponding phenylacetylene macrocycles, acetylene-bridged [2(n)]metacyclophanes, owing to the withdrawal of the electron density from the aromatic rings by the butadiyne linkages which facilitates pi-pi stacking interactions.     

One-pot synthesis of sialo-containing glycosyl amino acids by use of an N-trichloroethoxycarbonyl-beta-thiophenyl sialoside

We describe an efficient synthesis of 2,6- and 2,3-sialyl T antigens linked to serine in a one-pot glycosylation. We first investigated the glycosidation of thiosialosides by varying the N-protecting group. Modification of the C-5 amino group of beta-thiosialosides into the N-9-fluorenylmethoxycarbonyl, N-2,2,2-trichloroethoxycarbonyl (N-Troc), and N-trichloroacetyl derivatives enhanced the reactivity of these compounds towards glycosidation. Addition of a minimum amount of 3 A molecular sieves was also effective in improving the yield of alpha-linked sialosides. Next, we conducted one-pot syntheses of the glycosyl amino acids by using the N-Troc sialyl donor. The N-Troc derivative can be converted into the N-acetyl derivative without racemization of the amino acids. Branched-type one-pot glycosylation, initiated by regioselective glycosylation of the 3,6-dihydroxy galactoside with the N-Troc-beta-thiophenyl sialoside, provided the protected 2,6-sialyl T antigen in good yield. Linear-type one-pot glycosylation, initiated by chemoselective glycosylation of galactosyl fluoride with the N-Troc-beta-thiophenyl sialoside, afforded the protected 2,3-sialyl T antigen in excellent yield. Both protected glycosyl amino acids were converted into the fully deprotected 2,6- and 2,3-sialyl T antigens linked to serine in good yields.     

Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state

Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq=2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion.