Supramolecular FRET photocyclodimerization of anthracenecarboxylate with naphthalene-capped γ-cyclodextrin.
Supramolecular FRET photocyclodimerization of anthracenecarboxylate with naphthalene-capped γ-cyclodextrin.
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DOI：
10.3762/bjoc.7.38
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发表时间：
2011-03-07
影响因子：
2.7
通讯作者：
Inoue Y
中科院分区：
文献类型：
--
作者：
Wang Q;Yang C;Fukuhara G;Mori T;Liu Y;Inoue Y
合成了一种在γ-环糊精（CD）葡萄糖单元上锚定萘环的衍生物，研究了柔性和刚性封端对络合作用的影响，以及蒽羧酸（AC）环的Förster共振能量转移（FRET）和光手性行为.紫外-可见光谱、圆二色谱和荧光光谱研究表明，两个AC分子同时被包含在修饰的γ-CD空腔中，形成右旋螺旋，萘帽通过FRET机制有效地将单重态能量传递给包含在CD空腔中的AC。与天然γ-CD相比，修饰的γ-CD对AC表现出更高的第一结合常数（K1），但相对较低的第二结合常数（K2），导致总亲和力（K1 K2）增加一倍。与天然γ-CD相比，AC与这些修饰的γ-CD的光环化二聚产生更多的头对头（HH）二聚体，抗HH二聚体的对映体过量（ee）好得多。有趣的是，FRET激发进一步提高了抗HH二聚体的化学和光学产率高达36%和35%ee，其中CD腔内的高效FRET敏化，最大限度地减少了来自非手性“外部”光反应的“污染”，是负责的。FRET增敏也使我们能够实现与次当量的手性超分子主体的AC的催化光环化二聚。
γ-Cyclodextrin (CD) derivatives with a naphthalene moiety anchored to one or two of the glucose units of the CD were synthesized in order to investigate the effects of flexible and rigid capping upon complexation, as well as Förster resonance energy transfer (FRET) and photochirogenic behavior of anthracenecarboxylate (AC) moieties. UV–vis, circular dichroism and fluorescence spectral studies revealed that two AC molecules are simultaneously included in the modified γ-CD cavity to form a right-handed screw and also that the naphthalene cap efficiently transfers the singlet energy to AC included in the CD cavity via the FRET mechanism. Compared to native γ-CD, the modified γ-CDs showed much higher first association constants (K1) but relatively lower second association constants (K2) for AC, leading to two-fold larger overall affinities (K1K2). Photocyclodimerization of AC with these modified γ-CDs produced more head-to-head (HH) dimers in much better enantiomeric excesses (ee) for anti-HH dimer compared to native γ-CD. Interestingly, FRET excitation further enhanced the chemical and optical yields of anti-HH dimer up to 36% and 35% ee, for which the highly efficient FRET sensitization within the CD cavity, minimizing the “contamination” from the achiral “outside” photoreaction, is responsible. FRET sensitization also enabled us to achieve the catalytic photocyclodimerization of AC with a sub-equivalent amount of chiral supramolecular host.
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影响因子：
1.8
作者：
Yan, Cheng;Nishijima, Masaki;Inoue, Yoshihisa
通讯作者：
Inoue, Yoshihisa
影响因子：
15
作者：
Yang, Cheng;Mori, Tadashi;Inoue, Yoshihisa
通讯作者：
Inoue, Yoshihisa
影响因子：
15
作者：
Nakamura, A;Inoue, Y
通讯作者：
Inoue, Y
DOI：
10.1016/j.jphotochem.2005.04.017
发表时间：
2005-07-15
影响因子：
4.3
作者：
Yang, C;Fukuhara, G;Inoue, Y
通讯作者：
Inoue, Y
影响因子：
3.6
作者：
Yang, Cheng;Mori, Tadashi;Inoue, Yoshihisa
通讯作者：
Inoue, Yoshihisa