摘要
The eme reactions of α-ionones with singlet oxygen were examined to ascertain the effect of secondary Me interaction between the reactants on the reaction regiospecificity. Exclusive formation of 3-hydroxy-γ-ionones found in the reactions reveals favorable interaction of singlet oxygen with the acyclic α-hydrogen atom,On the other hand,no formation of 3-hy- droxy-β-ionones implies that the steric requirement was not met for the bond formation between zwitterionic perepoxide with C_1-hydrogen in the process.The MMP21 and MNDO calculations indicate minus value of the secondary interaction energy for the aeyelie α-hydrogen abstrac- tion and a repulsion between the oxygen with C_1-hydrogen atom.Twisting tilting of the double bond may account for favorable attack of singlet oxygen on C_3.An explanation of the excellent regiospecificity was addressed and placed in proper mechanic prospective.
The eme reactions of α-ionones with singlet oxygen were examined to ascertain the effect of secondary Me interaction between the reactants on the reaction regiospecificity. Exclusive formation of 3-hydroxy-γ-ionones found in the reactions reveals favorable interaction of singlet oxygen with the acyclic α-hydrogen atom,On the other hand,no formation of 3-hy- droxy-β-ionones implies that the steric requirement was not met for the bond formation between zwitterionic perepoxide with C_1-hydrogen in the process.The MMP21 and MNDO calculations indicate minus value of the secondary interaction energy for the aeyelie α-hydrogen abstrac- tion and a repulsion between the oxygen with C_1-hydrogen atom.Twisting tilting of the double bond may account for favorable attack of singlet oxygen on C_3.An explanation of the excellent regiospecificity was addressed and placed in proper mechanic prospective.
基金
project supported by the National Natural Science Foundation of China.
