A new reaction of vicinal sulfonyliminocarboxylates with phosphites

The reaction of alkyl trifluoro(organylsulfonylimino)propionates with phosphites occurs with NC transfer of the RSO₂ group and leads to sulfonyl-substituted trifluoroalanine derivatives. The novel rearrangement is interpreted as cheletropic 1,4-cycloaddition of the phosphite and subsequent 1,2-shift of the sulfonyl group in the intermediate cyclic phosphorane.     

Regioselective 1,4-trifluoromethylation of α,β-enones using ‘protect-in-situ’ methodology

In a convenient and efficient procedure, the nucleophilic 1,4-trifluoromethylation of several α,β-enones using (trifluoromethyl)trimethylsilane was achieved. The high regioselectivity of the reaction has been reached by blocking the carbonyl moiety of the electrophile with a bulky aluminum-centered Lewis acid.     

Electron transfer induced dissociations of 2- and 4-alkyl cyclohexadienones

Several 2- and 4-alkylcyclohexadienones were prepared and shown to accept electrons to produce ketyl radical anions that dissociated rapidly at room temperature to release carbon-centered radicals and an aromatic phenoxide type anion. In the PET process with benzyl-substituted cyclohexadienones, initiated with triethylamine, the benzyl radicals dimerised or abstracted an H-atom from solvent. In electrochemical reductions, and in reductions with alkali metals in liquid ammonia, the benzyl radicals were further reduced to anions.     

Microwave-accelerated conjugate addition of aldehydes to α,β-unsaturated ketones

Aldehydes undergo smooth conjugate addition to α,β-unsaturated ketones in the presence of 5-(2-hydroxyethyl)-1,3-thiazolium halides and DBU adsorbed onto the surface of basic alumina under microwave irradiation and solvent-free conditions to afford 1,4-diketones in enhanced yields and reduced reaction times compared to conventional methods.     

Addition of Bromotrichloromethane and Tetrachloromethane to cis-Cyclooctene,Cyclohexene, and Norbornadiene in the Presence of Palladium(II) Complexes

Addition of bromotrichloromethane and tetrachloromethane to alkenes in the presence of palladium(II) complexes begins with single-electron transfer from the palladium atom to polyhalomethane molecule, followed by fragmentation of the radical anion thus formed and generation of trichloromethyl radical. Halogen transfer to a carbon-centered radical arising from addition of trichloromethyl radical at the double bond occurs both from the polyhalomethane molecule and from halide palladium complex.     

Synthesis and Structure of Mixed Phosphonium-iodonium Ylide

A mixed phosphonium-iodonium ylide, phenyliodoniumethoxycarbonylmethylenetriphenylphosphorane borofluoride, was synthesized. Its structure was established by means of X-ray diffraction analysis. Temperature dependence of ¹H, ¹³C, and ³¹P spectra of the ylide synthesized was investigated. A dynamic equilibrium between Z and E-isomers was observed.