RESUMO
Autoxidation limits the longevity of essentially all hydrocarbons and materials made therefrom - including us. The radical chain reaction responsible often leads to complex mixtures of hydroperoxides, alkyl peroxides, alcohols, carbonyls and carboxylic acids, which change the physical properties of the material - be it a lubricating oil or biological membrane. Autoxidation is inhibited by addtitives such as radical-trapping antioxidants, which intervene directly in the chain reaction. Herein we review the most salient features of autoxidation and its inhibition, emphasizing concepts and mechanistic considerations important in understanding this chemistry across the wide range of contexts in which it is relevant.
RESUMO
Pyridinyl amide ion pairs carrying various electron-withdrawing substituents were synthesized with selected ammonium or phosphonium counterions. Compared to neutral pyridine-based organocatalysts, these new ion pair Lewis bases display superior catalytic reactivity in the reaction of isocyanates with alcohols and the aza-Morita-Baylis-Hillman reaction of hindered electrophiles. The high catalytic activity of ion pair catalysts appears to be due to their high Lewis basicities toward neutral electrophiles as quantified through quantum chemically calculated affinity data.
RESUMO
We present the synthesis and the photochemical and catalytic switching properties of an azopyridine as a photoswitchable ligand, covalently attached to a Ni(II)-porphyrin. Upon irradiation with 530 nm (green light), the azopyridine switches to the cis configuration and coordinates with the Ni2+ ion. Light of 435 nm (violet) isomerizes the ligand back to the trans configuration, which decoordinates for steric reasons. This so-called record player design has been used previously to switch the spin state of Ni2+ between singlet and triplet. We now use the coordination/decoordination process to switch the catalytic activity of the dimethylaminopyridine (DMAP) unit. DMAP is a known catalyst in the nitroaldol (Henry) reaction. Upon coordination to the Ni2+ ion, the basicity of the pyridine lone pair is attenuated and hence the catalytic activity is reduced. Decoordination restores the catalytic activity. The rate constants in the two switching states differ by a factor of 2.2, and the catalytic switching is reversible.
RESUMO
The mechanism of the oligomerization of aliphatic isocyanates catalyzed by trialkylphosphanes has been studied through low temperature 31 P and 15 Nâ NMR spectroscopy combined with computational chemistry. A revised mechanism is proposed that contains several (spiro)cyclic pentacoordinate phosphorous intermediates. Previously reported spectroscopic data of a transient intermediate has been reevaluated and assigned to a cyclic intermediate containing a P-N bond by experiments with 15 N-labeled isocyanate. 13 C, 15 N, and 31 Pâ NMR shifts that support this assignment have been calculated using quantum chemical methods.
RESUMO
Chloro-substituted triethylsilyl enol ethers derived from cyclohexanone and related ketones are converted with aluminum powder in the presence of indium trichloride to functionalized allylic aluminum reagents which represent a new type of synthetic equivalent of metal enolates. These allylic organometallics undergo highly diastereoselective additions to aldehydes and methyl aryl ketones, giving aldol products with a ß-quaternary center.