An asymmetric Heck reaction allows desymmetrization of substituted cyclic olefins in high dr and ee. A bisphosphine oxide is uniquely stereoselective for this purpose. Desymmetrization of bicyclic olefins via hydroarylation can also be realized in high ee.

As a typical example of screening for a microbial biocatalyst from nature, isolation of aldoxime-degrading microorganisms, characterization of a new enzyme phenylacetaldoxime dehydratase, and application of this enzyme to nitrile synthesis are described. The pathway in which aldoximes are successively degraded via nitrile in microorganisms could be named as 'aldoxime-nitrile pathway'. As an exa...

We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

A nitrile utilizing bacterium Rhodococcus sp. MTB5 was previously isolated in our laboratory by the enrichment culture technique. It is able to utilize butyronitrile as sole carbon, nitrogen, and energy source. Maximum butyronitrile degrading property of this strain has been investigated. Results reveal that 100, 98, and 88 % degradation was achieved for 2, 2.5, and 3 % butyronitrile, respectiv...

We report the direct observation of a bent geometry for a nonstabilized nitrile imine in a metal-coordination crystal. The photoinduced tetrazole ring rupture to release N(2) appears to depend on the size of voids around the N(3)-N(4) bond in the crystal lattice. We further observed the selective formation of the 1,3-addition product when a reactive nitrile imine was photogenerated in water. Ov...

The bacterial strain Rhodococcus butanica (ATCC 21197), which exhibits nitrilase and nitrile hydratase/amidase activities, catalyses the enantioselective hydrolysis of racemic naproxen nitrile (R/S)-1 to furnish a moderate enantiomeric excess of (S)-naproxen (S)-3. Racemic naproxen amide (R/S)-2 is not a good substrate for this strain. Resting cells of the newly selected bacterial strain Rhodoc...

Multinuclear and dendritic iron-nitrile piano-stool cationic complexes were synthesized in quantitative yield by a single-step synthesis involving visible-light photolysis of the complex [CpFe(eta(6)-toluene)][PF6]. This synthetic strategy was applied to mono-, bis- and tris-nitrile ligands and to new nitrile-terminated dendrimers containing 9, 27, and 81 tethers. All the synthesized products a...

Four novel phosphine-substituted ruthenium(ii) polypyridine complexes with nitrogen oxides-trans(P,NO2)-[Ru(trpy)(Pqn)(NO2)]PF6 (trans-NO2), cis(P,NO2)-[Ru(trpy)(Pqn)(NO2)]PF6 (cis-NO2), [Ru(trpy)(dppbz)(NO2)]PF6 (PP-NO2), and cis(P,NO)-[Ru(trpy)(Pqn)(NO)](PF6)3 (cis-NO)-were synthesised (trpy = 2,2':6',2''-terpyridine, Pqn = 8-(diphenylphosphanyl)quinoline, and dppbz = 1,2-bis(diphenylphosphan...

Glucoraphanin in Brassica vegetables breaks down to either sulforaphane or sulforaphane nitrile depending on the conditions, and sulforaphane can be further conjugated with glutathione. Using a high-throughput microtitre plate assay and TaqMan real time quantitative RT-PCR to measure mRNA, we show that sulforaphane and its glutathione conjugate, but not the nitrile, increased significantly (P <...