The magnitude of the membrane dipole field was measured using vibrational Stark effect (VSE) shifts of nitrile oscillators placed on the unnatural amino acid p-cyanophenylalanine (p-CN-Phe) added to a peptide sequence at four unique positions. These peptides, which were based on a repeating alanine-leucine motif, intercalated into small unilamellar DMPC vesicles which formed an α-helix as confi...

Organofluorine compounds have become important building blocks for a broad range of advanced materials, polymers, agrochemicals, and increasingly for pharmaceuticals. Despite tremendous progress within the area of fluorination chemistry, methods for the direct introduction of fluoroalkyl-groups into organic molecules without prefunctionalization are still highly desired. Here we present a conce...

The photolysis at 222 nm of 5-methyltetrazole isolated in a cryogenic argon matrix leads to formation of methyl nitrile imine as primary product. Subsequent irradiation at 328 nm induces transformation of the nitrile imine into 4π-electron three-membered-ring 3-methyl-1H-diazirine, which photorearranges to give methyl carbodiimide. These products were characterized by IR spectroscopy and theore...

Difluoromethylation on sp(3) carbon of various nitrile compounds with lithium base and fluoroform (CF3H), which is an ideal difluoromethylating reagent, is shown to provide the α-difluoromethylated nitrile products with an all-carbon quaternary center in moderate to high yields. The Ruppert-Prakash reagent (CF3TMS) is also applicable to the reaction, affording the α-siladifluoromethylated nitri...

The title compound, C(12)H(15)N(5)OS, was obtained by reaction of 2-(2-(methyl-thio)pyrimidin-4-yl)-3-oxopropane-nitrile with (tetra-hydro-furan-3-yl)hydrazine dihydro-chloride, and the racemic product was subsequently separated by chiral chromatography (first peak; [α](D) (20) = +51.3°). The chiral center at the substituted atom of the tetra-hydro-furanyl group has an R-configuration. The pyri...

Vibrational Stark effect spectroscopy was used to measure electrostatic fields in the hydrophobic region of the active site of human aldose reductase (hALR2). A new nitrile-containing inhibitor was designed and synthesized, and the X-ray structure of its complex, along with cofactor NADP(+), with wild-type hALR2 was determined at 1.3 Å resolution. The nitrile is found to be in the proximity of ...