Meta- or para-nitro-(pentafluorosulfonyl)benzenes underwent the Davis reaction with arylacetonitriles to provide the SF5-containing benzisoxazoles. Good yields were obtained with arylacetonitriles containing the electron-neutral or electron-donor group, while those with the electron-acceptor group were found to be unreactive. Reductions of the benzisoxazoles gave ortho-aminobenzophenones in hig...

An efficient and convenient protocol for the synthesis of 2H-chromenones has been developed. In the presence of tBuOK in DMF, good to excellent yields of various chromenones were obtained from the corresponding salicylaldehydes and arylacetonitriles. No protection of inert gas atmosphere is required here.

The gene encoding an enantioselective arylacetonitrilase was identified on a 3.8 kb DNA fragment from the genomic DNA of Pseudomonas fluorescens EBC191. The gene was isolated, sequenced and cloned into the L-rhamnose-inducible expression vector pJOE2775. The nitrilase was produced in large quantities and purified as a histidine-tagged enzyme from crude extracts of L-rhamnose-induced cells of Es...

Investigation of central nervous system activity of phenylcyclohexylamines was continued by preparation of "reversed" analogues. Following the unexpected finding of analgesic activity with 1-(dimethylamino)-1-phenylcyclohexylamine, the SAR of the series was investigated. Synthesis starts by double Michael reaction of acrylate on arylacetonitriles. Following cyclization, decarboxylation, ketaliz...

The very high mono-C-methylation selectivity (>99%) of arylacetic acid derivatives (ArCH2X; X = CN, CO2Me) with dimethyl carbonate (DMC) is due to a mechanism that involves consecutive methoxycarbonylation, methylation, and demethoxycarbonylation steps. Important aspects of this mechanism are clarified herein by a kinetic investigation. In the case of arylacetonitriles, at 140 degrees C, the co...

[reaction: see text] There have been a number of reports of the kinetic conjugate (1,4) addition of metalated arylacetonitriles to enones. Several proposals have been made to explain this behavior based on nucleophile structure or aggregation state or on the HSAB properties of the reactants. A reexamination of these studies showed that in each case the 1,4 adducts resulted from equilibration of...