Enantiodifferentiation in the Photoisomerization of (Z,Z)-1,3-Cyclooctadiene in the Cavity of gamma-Cyclodextrin-Curcubit[6]uril-Wheeled [4]Rotaxanes with an Encapsulated Photosensitizer
Enantiodifferentiation in the Photoisomerization of (Z,Z)-1,3-Cyclooctadiene in the Cavity of gamma-Cyclodextrin-Curcubit[6]uril-Wheeled [4]Rotaxanes with an Encapsulated Photosensitizer
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γ-环糊精-葫芦[6]脲轮[4]轮烷空腔中(Z,Z)-1,3-环辛二烯与封装光敏剂光异构化的对映分化
DOI：
10.1021/acs.orglett.7b00057
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发表时间：
2017
期刊：
影响因子：
5.2
通讯作者：
Yang Cheng
中科院分区：
文献类型：
--
作者：
Yan Zhiqiang;Huang Qinfei;Liang Wenting;Yu Xingke;Zhou Dayang;Wu Wanhua;Chruma Jason J.;Yang Cheng
将联苯型光敏剂轴注入到天然γ-环糊精和加帽γ-环糊精的空腔中，并采用1,3偶极环加成的方式进行轮烷化反应，构建了高度明确的手性结合/敏化位点。通过核磁共振、紫外-可见、圆二色性和荧光光谱研究，研究了基态和激发态的轴和盖部分的取向和相互作用。（Z，Z）-1,3-环- ctadiene在这些[4]轮烷腔内的原位光异构化产生（Z，E）-1,3-环- ctadiene高达15.3%的ee，这代表了迄今为止这种超分子光致作用获得的最高水平的对映分化。
A biphenyl photosensitizer axle was implanted into the cavities of native and capped γ-cyclodextrins through rotaxanation using a cucubit[6]uril-templated azide–alkyne 1,3-dipolar cycloaddition, resulting in the construction of highly defined chiral binding/sensitizing sites. The orientation and interaction of the axle and capping moieties at the ground and excited states were interrogated by NMR, UV–vis, circular dichroism, and fluorescence spectroscopic studies. In situ photoisomerization of (Z,Z)-1,3-cyclooctadiene sensitized in the cavity of these [4]rotaxanes afforded (Z,E)-1,3-cyclooctadiene in up to 15.3% ee, which represents the highest level of enantiodifferentiation obtained to date for this supramolecular photochirogenesis.