Enantiodifferentiating Z-E photoisomerization of cyclooctene sensitized by chiral polyalkyl benzenepolycarboxylates
Enantiodifferentiating Z-E photoisomerization of cyclooctene sensitized by chiral polyalkyl benzenepolycarboxylates
复制标题
手性多烷基苯多羧酸盐敏化环辛烯的对映分化 Z-E 光异构化
DOI：
--
复制
发表时间：
1992
期刊：
影响因子：
--
通讯作者：
A. Tai
中科院分区：
文献类型：
--
作者：
Y. Inoue;N. Yamasaki;Taizo Yokoyama;A. Tai
通过手性多烷基苯多羧酸酯的单重态光敏化，实现了环辛烯(1)的高效、独特的Z-E对映异构化反应。光学产率的转化率依赖关系和外消旋(E)-异构体1E的动力学拆分明确地表明，对映体分化步骤不是手性增敏剂与对映体1E的初始猝灭，而是平面1Z在与手性增敏剂的单重态激基缔合物中向扭曲的单重态环辛烯(1 P)的旋转弛豫
Highly efficient and unique enantiodifferentiating Z-E photoisomerization of cyclooctene (1) was achieved through singlet photosensitization with chiral polyalkyl benzenepolycarboxylates. Conversion dependence of optical yields and an attempted kinetic resolution of racemic (E)-isomer 1E unequivocally showed that the enantiodifferentiating step is not the initial quenching of chiral sensitizer with enantiomeric 1E but the rotational relaxation of planar 1Z to twisted singlet cyclooctene ( 1 p) within the singlet exciplex with chiral sensitizer