Manipulating gamma-cyclodextrin-mediated photocyclodimerization of anthracenecarboxylate by wavelength, temperature, solvent and host
Manipulating gamma-cyclodextrin-mediated photocyclodimerization of anthracenecarboxylate by wavelength, temperature, solvent and host
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通过波长、温度、溶剂和主体操纵γ-环糊精介导的蒽甲酸酯光环二聚反应
DOI：
10.1039/c3pp50255d
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发表时间：
2014
影响因子：
3.1
通讯作者：
Inoue Yoshihisa
中科院分区：
文献类型：
--
作者：
Yang Cheng;Wang Qian;Yamauchi Masahito;Yao Jabing;Zhou Dayang;Nishijima Masaki;Fukuhara Gaku;Mori Tadashi;Liu Yu;Inoue Yoshihisa
研究了波长对2-蒽甲酸（AC）在天然和修饰γ-环糊精（CD）作用下，在不同溶剂和不同温度下光致二聚化反应的影响，以控制AC与CD在基态2：1络合时的光手性结果.实际上，立体化学结果，即顺式/反式、头-尾/头-头（HT/HH）和特别是对映异构体比率，是照射波长的关键函数，而与所采用的CD主体无关。此外，观察到的波长效应强烈依赖于主机结构，反应温度和溶剂，其中改变堆叠几何形状的复杂的AC对被认为是负责。通过优化照射波长、手性主体、温度和溶剂，手性顺式HT和反式HH二聚体的对映体过量分别达到54%和−37%。
Wavelength effects on the enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate (AC) mediated by native and modified γ-cyclodextrins (CDs) were examined in different solvents at varying temperatures to manipulate the photochirogenic outcomes beyond the thermodynamically determinedre/si-enantiotopic face selectivity upon 2:1 complexation of AC with CD in the ground state. Indeed, the stereochemical outcomes,i.e. syn/anti,head-to-tail/head-to-head(HT/HH) and in particular enantiomer ratios, were critical functions of the irradiation wavelength, irrespective of the CD host employed. Furthermore, the wavelength effects observed strongly depended on the host structure, reaction temperature and solvent employed, for which altered stacking geometry of the complexed AC pair is thought to be responsible. By optimizing the irradiation wavelength, chiral host, temperature and solvent, an enantiomeric excess of up to 54 and −37% were achieved for chiralsyn-HT andanti-HH dimers.