The slippery potential energy surface of aryl nitrenes has revealed unexpected and fascinating reactions. To explore such a challenging surface, one powerful approach is to use a combination of a cryogenic matrix environment and a tunable narrowband radiation source. In this way, we discovered the heavy-atom tunneling reaction involving spontaneous ring expansion of a fused-ring benzazirine int...

A combination of experimental methods, photoelectron-imaging spectroscopy, flowing afterglow-photoelectron spectroscopy and the flowing afterglow-selected ion flow tube technique, and electronic structure calculations at the B3LYP/6-311++G(d,p) level of density functional theory (DFT) have been employed to study the mechanism of the reaction of the hydroxide ion (HO-) with 1H-1,2,3-triazole. Fo...

Transition-metal-catalyzed [4+2] heteroannulation of α,β-unsaturated oximes and their derivatives with alkynes has been developed into a powerful strategy for the synthesis pyridines. It nevertheless lacks regioselectivity when unsymmetrically substituted are used. We report herein unprecedented polysubstituted pyridines by formal [5+1] two readily accessible building blocks. A copper-catalyzed...

Hydroxyacetonitrile is a simple derivative of methanol. This molecule has a strong astrophysical interest. In astrophysical environment, the formation of hydroxyacetonitrile (HOCH2CN), has been shown to compete with aminomethanol (NH2CH2OH), a glycine precursor, through the Strecker synthesis. in addition its photochemistry leads to the formation of formylcyanide (CHOCN), ketenimine (CH2CNH), f...

The aim of this study was to investigate the behavior of the protonated paralytic shellfish poisons saxitoxin (STX) and neosaxitoxin (NEO) in the gas-phase after ion activation using different tandem mass spectrometry techniques. STX and NEO belong to a group of neurotoxins produced by several strains of marine dinoflagellates. Their chemical structures are based on a tetrahydropurine skeleton ...

The unimolecular photochemistry of 3,5-dimethylisoxazole (1) induced by a narrow-band tunable UV laser was studied using low-temperature matrix isolation coupled with infrared spectroscopy. Monomers of 1 were isolated in argon matrices at 15 K and characterized spectroscopically. Irradiation of matrix-isolated 1 at λ = 222 nm (near its absorption maximum) led to the corresponding 2H-azirine 3 a...