Efficient biocatalysis for the production of enantiopure (S)-epoxides using a styrene monooxygenase (SMO) and Leifsonia alcohol dehydrogenase (LSADH) system

Herein we report the production of enantiopure epoxides through biocatalysis using recombinant Escherichia coli cells expressing Rhodococcus sp. ST-10 styrene monooxygenase (SMO) and Leifsonia sp. S749 alcohol dehydrogenase (LSADH) genes are described. Rhodococcus sp. ST-10 SMO catalyzed the epoxidation of various alkenes, including styrene derivatives, vinyl pyridines, and linear alkenes, to give (S)-epoxides. NADH was regenerated by the reduction of NAD⁺ by LSADH with 2-propanol. The E. coli biocatalyst was used in an aqueous/organic biphasic reaction system and the reaction conditions were optimized. Under the optimized conditions, 170 mM of (S)-styrene oxide was obtained from styrene in the organic phase with excellent enantiomeric excess (99.8%). This biocatalytic process was used to synthesize various (S)-epoxides.     

Molecular Chirality Recognized by Achiral Compounds

Abstract

Three cases are described where chirality is recognized by achiral molecules, where chirality is induced into achiral compounds through interactions with chiral compounds, and lastly where induced chirality in the solid-state is utilized for an enantio-selective photoreaction. In the first instance, the thermodynamically and kinetically preferred diastereoisomer of an optically labile chromium complex depended on the nature of the achiral solvent. In the second case, for the first time 1,2-chloroethane was trapped and observed in a chiral near-eclipsed form and 1-chloropropane in the truly eclipsed form at room temperature in a 1:1 inclusion complex with an optically active host molecule. Finally, induced chirality in a prochiral compound in the solid-state was successfully employed in an enantio-selective photoreaction. In the two cases, solid-state CD provided valuable information.     

Two-dimensional network formation of cardiac myocytes in agar microculture chip with 1480 nm infrared laser photo-thermal etching

We have developed a new method that enables agar microstructures to be used to cultivate cells and that allows cell network patterns to be controlled. The method makes use of non-contact three-dimensional photo-thermal etching with a 1480 nm infrared focused laser beam, which is strongly absorbed by water and agar gel, to form the shapes of agar microstructures. It allows microstructures to be easily formed in an agar layer within a few minutes, with cell-culture holes formed by the spot heating of a 100 mW laser and tunnels by the tracing of a 100 microm s(-1), 40 mW laser. We cultivated rat cardiac myocytes in adjacent microstructures and observed synchronized beating in them 90 min after they had made physical contact. Our results indicate that the system can make and use microstructures for cell-network cultivation in a minimal amount of time without any expensive microfabrication facilities or complicated procedures.     

Synthetic studies directed toward the assembly of the C-glycoside fragment of the telomerase inhibitor D8646-2-6

[reaction: see text] Construction and characterization of the C-glycosidic moiety of telomerase inhibitor D8646-2-6 (1) are described. This is the first example of the C-glycosylation using electron-poor aromatics, 4-hydroxypyrone, as a glycosyl acceptor. The glycosylation reaction and base-promoted isomerization affords desired beta-C-glycoside in a 61% overall yield.     

Formal [4+2] cycloaddition of 3-phenylcyclobutanones with nitriles

Various 3-phenylcyclobutanones reacted with aliphatic and aromatic nitriles in the presence of Me₃SiOTf to afford dihydropyridones by formal [4+2] cycloaddition.     

1,4-Dehydrogenation with a Two-Coordinate Cyclic (Alkyl)(amino)silylene

Cyclic (alkyl)(amino)silylene (CAASi) 1 has been found to successfully dehydrogenate 1,4-dihydroaromatic compounds containing various substituents to afford the corresponding aromatic compounds. The observed high substrate generality proves 1 to be a potential 1,4-dehydrogenation reagent for organic compounds. For the reaction with 9,10-dimethyl-9,10-dihydroanthracene, silylene 1 activated not only benzylic C−H bonds but also aromatic C−H bonds to yield a silaacenaphthene derivative, which is an unprecedented reaction of silylenes. The results of the experimental and computational study of the reaction of CAASi 1 with 9,10-dihydroanthracene and 1,4-cyclohexadiene are consistent with the notion that 1,4-dehydrogenation with CAASi 1 proceeds mainly through a stepwise hydrogen-abstraction mechanism.     

A novel transformation of a 1 : 1 : 1 racemic complex of 2,2'-dihydroxy-1,1'-binaphthyl, Me4N+ Cl- and MeOH into a conglomerate in the solid state by heating or contact with MeOH vapour

The title racemate-to-conglomerate transformation which occurs in the solid state on heating or contact with MeOH vapour has been studied by IR and DTA spectral measurements, microscopic observation, and by X-ray structural and X-ray powder diffraction analysis.