RESUMO
A straightforward synthesis of 1,2-dicyanoalkanes by reacting nitroalkenes with trimethylsilyl cyanide in the presence of tetrabutylammonium fluoride is described. The reaction proceeds through a tandem double Michael addition under mild conditions. Employing the hypervalent silicate generated from trimethylsilyl cyanide and tetrabutylammonium fluoride is essential for achieving this transformation. Mechanistic studies suggest that a small amount of water included in the reaction media plays a key role. This protocol is applicable to various types of substrates including electron-rich and electron-deficient aromatic nitroalkenes, and aliphatic nitroalkenes. Moreover, vinyl sulfones were found to be good alternatives, particularly for electron-deficient nitroalkenes. The broad substrate scope and functional group tolerance of the reaction makes this approach a practical method for the synthesis of valuable 1,2-dicyanoalkanes.
RESUMO
An efficient, unique, and convenient method for the iodoamidation of olefins with chloramine salts and I(2) in aqueous media is described. This method was applicable to a wide range of olefins, including aromatic, aliphatic, and electron-deficient olefins.
RESUMO
The carbon dioxide (CO(2))-induced amidobromination of olefins with bromamine-T is described. The method can be used in reactions with a wide range of olefins, both aromatic and aliphatic, as well as electron-rich and deficient olefins, leading to the regioselective formation of amidobrominated compounds.
Assuntos
Alcenos/química , Dióxido de Carbono/química , Halogenação , Sulfonamidas/química , Catálise , Estereoisomerismo , Especificidade por SubstratoRESUMO
Photochemical properties of trans-3,3',5,5'-tetramethoxystilbene (TMST) have been studied in various polar solvents. The Stokes shift of trans-TMST was found to be increased with increasing solvent polarity. The fluorescence lifetime of trans-TMST experienced a large solvent effect changing from 2.3 ns in cyclohexane to 16.6 ns in acetonitrile. These results indicate that the excited singlet state of trans-TMST has a charge-transfer (CT) character. On the basis of the obtained results, the interior polar environment of a water-soluble TMST dendrimer is discussed.
RESUMO
Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site. Subsequent hole transfer from the trapping site to the core ST generated ST*+. The shielding effects of D depending on the dendrimer generation on the growth and decay of ST*+ were observed. It was revealed for the first time that D acts as the hole trapping site and the hole conductor on the way of the exothermic hole transfer from the terminal of D to the central core ST. We also found that D inhibits the charge recombination with 9,10-dicyanoanthracene radical anion because of the steric hindrance.
RESUMO
The two-photon ionization (TPI) process (308 and 266 nm) of stilbene dendrimers having a stilbene core and benzyl ether type dendrons has been investigated in an acetonitrile and 1,2-dichloroethane mixture (3:1) in order to elucidate the dendrimer effects. The quantum yield of the formation of stilbene core radical cation during the 308-nm TPI was independent of the dendron generation of the dendrimers, whereas a generation dependence of the quantum yield of the radical cation was observed during the 266-nm TPI, where both the stilbene core and benzyl ether type dendron were ionized, suggesting that the subsequent hole transfer occurs from the dendron to the stilbene core, and that the dendron acts as a hole-harvesting antenna. The neutralization rate of the stilbene core radical cation with the chloride ion, generated from the dissociative electron capture by 1,2-dichloroethane, decreased with the increase in the dendrimer generation, suggesting that the dendron is an effective shield of the stilbene core radical cation against the chloride ion.
RESUMO
The third generation of novel photo-responsive water-soluble stilbene dendrimer (trans- and cis-G3 WSD) undergoes unusual one-way trans-to-cis isomerization to give 100% of cis isomer at the photostationary state on UV irradiation in water.