Inclusion of alkyl nitriles by tetra-armed cyclens with styrylmethyl groups
Inclusion of alkyl nitriles by tetra-armed cyclens with styrylmethyl groups
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DOI：
10.1039/d0dt00335b
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发表时间：
2020-03-14
影响因子：
4
通讯作者：
Habata, Yoichi
中科院分区：
文献类型：
--
作者：
Ju, Huiyeong;Tenma, Honoka;Habata, Yoichi
报道了以苯乙烯甲基为侧臂的四臂环戊二烯（2a-2 e）及其Ag+配合物的合成。Ag+配合物与四苯乙烯甲基臂大环戊二烯（2a）纳入烷基腈的伪腔形成的四个苯乙烯甲基侧臂。这促使我们将该系统应用于确定具有低[α]（D）和低圆二色性（CD）强度的手性腈的绝对构型。在2a/Ag+配合物的圆二色光谱中，（S）-和（R）-G1没有表现出特异的Cotton效应，而当手性腈加入到2a/Ag+配合物中时，观察到剧烈的光谱变化。（S）-G1@2a/Ag+系统表现出先负后正的Cotton效应，而（R）-G1@2a/Ag+系统则表现出（S）-G1@2a/Ag+的Cotton效应的镜像。因此，我们已经证明了一种新的技术，用于确定弱旋光分子的绝对配置使用Ag+配合物与2a。
Synthesis of tetra-armed cyclens (2a-2e), with substituted styrylmethyl groups as side-arms, and their Ag+ complexes is reported. The Ag+ complex with a tetra styrylmethyl-armed cyclen (2a) incorporates alkyl nitriles in a pseudo-cavity formed by the four styrylmethyl side-arms. This prompted us to apply this system to the determination of the absolute configurations of chiral nitriles with low [alpha](D) and low circular dichroism (CD) intensity. In the CD spectra of the 2a/Ag+ complex, (S)- and (R)-G1 did not show a specific Cotton effect, while when chiral nitriles were added to the 2a/Ag+ complex, drastic spectral changes were observed. The (S)-G1@2a/Ag+ system exhibited first a negative and then a positive Cotton effect, whereas the (R)-G1@2a/Ag+ system showed the mirror image of the Cotton effect of (S)-G1@2a/Ag+. We have, therefore, demonstrated a new technique for determining the absolute configurations of weak optical rotation molecules using the Ag+ complex with 2a.