481633-07-2Relevant articles and documents
Mechanism of an alcohol-trapping reaction in the direct and benzophenone-sensitized photodenitrogenation of a spiroepoxy-substituted azoalkane: Solvent effects and stereochemical deuterium labeling
Abe, Manabu,Adam, Waldemar,Minamoto, Takafumi,Ino, Yasunori,Nojima, Masatomo
, p. 1796 - 1803 (2003)
The spin-state-dependent reactivity, singlet versus triplet, of the 2-spiroepoxy-1,3-cyclopentane-1,3-diyl DR2 has been assessed through alcohol-trapping reactions for which the effect of solvent acidity on the product distribution of the alcohol trapping products 2 versus 3 + 4 and stereochemical deuterium-labeling studies have been performed. The proposed mechanism for the solvent effect on the product ratio (2/3 + 4) reveals the importance of the hydrogen-bonded intermediates I1 and I2 in the trapping reactions; the stereochemical deuterium-labeling results clarify the dipole structure trapped by the alcohol. The dipoles DP1 and DP2, in which the configuration between the epoxide oxygen and the deuterium atoms is retained, are inferred for the direct photodenitrogenation reactions (singlet state), whereas for the benzophenone-sensitized photoreactions (triplet state), after ISC, the ring-opened dipole DP3 is implied as the intermediate that is trapped by the alcohol.
Reaction of 7,7-diphenyl-6-oxabicyclo[3.2.0]hept-1-ene with ROH; controlling factors on the regioselectivity in the nucleophilic addition reaction
Abe, Manabu,Minamoto, Takafui,Ino, Yasunori,Kawakami, Takanori,Nojima, Masatomo
, p. 7043 - 7047 (2007/10/03)
ROH-induced decomposition of the strained 7,7-diphenyl-6-oxabicyclo[3.2.0]hept-1-ene 1 was investigated in detail. The selective formation of the endo double-bonded alkene 3 was observed for the reaction with H2O or MeOH. Alternatively, the rea
