Synthesis, pi-Face-Selective Aggregation, and pi-Face Chiral Recognition of Configurationally Stable C3-Symmetric Propeller-Chiral Molecules with a pi-Core
Synthesis, pi-Face-Selective Aggregation, and pi-Face Chiral Recognition of Configurationally Stable C3-Symmetric Propeller-Chiral Molecules with a pi-Core
复制标题
具有 pi 核的构型稳定的 C3 对称螺旋桨手性分子的合成、pi 面选择性聚集和 pi 面手性识别
DOI：
10.1002/chem.201400094
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
Masahiko Yamaguchi
中科院分区：
文献类型：
--
作者：
Nozomi Saito;Ryo Terakawa;Masahiko Yamaguchi
在光学纯态下合成了具有垂直于C3轴的平面π核的C3对称的螺旋桨-手性化合物(P，P，P)-1和(M，M，M)-1。(P，P，P)-1具有两个不同高度的螺旋桨-手性π面，分别称为(P/L)面和(P/H)面。由于π-核心中包含的螺烯的刚性结构，每个面的构型都是稳定的。~1H 核磁共振、CD、UV/Vis光谱和水汽压渗透压分析表明，(P，P，P)-1在有机溶液中形成二聚体。X-射线单晶分析表明，固相中存在(P/L)/(P/L)相互作用，而溶液中的(P/H)/(P/H)和(P/L)/(P/H)相互作用也以(P/L)/(P/H)为主。外消旋混合物的二聚化常数表明，杂手性(P，P，P)-1/(M，M，M)-1相互作用远弱于同手性(P，P，P)-1/(P，P，P)-1相互作用。结果表明，螺旋桨-手性(P/L)面与(P/L)面的相互作用比(P/H)面、(M/L)面和(M/H)面更强。研究表明，构型稳定的螺旋桨-手性分子具有π-Face选择性聚集和π-Face手性识别能力。
TheC3‐symmetric propeller‐chiral compounds (P,P,P)‐1and (M,M,M)‐1with planar π‐cores perpendicular to theC3‐axis were synthesized in optically pure states. (P,P,P)‐1possesses two distinguishable propeller‐chiral π‐faces with rims of different heights named the (P/L)‐face and (P/H)‐face. Each face is configurationally stable because of the rigid structure of the helicenes contained in the π‐core. (P,P,P)‐1formed dimeric aggregates in organic solutions as indicated by the results of1H NMR, CD, and UV/Vis spectroscopy and vapor pressure osmometry analyses. The (P/L)/(P/L) interactions were observed in the solid state by single‐crystal X‐ray analysis, and they were also predominant over the (P/H)/(P/H) and (P/L)/(P/H) interactions in solution, as indicated by the results of1H and 2D NMR spectroscopy analyses. The dimerization constant was obtained for a racemic mixture, which showed that the heterochiral (P,P,P)‐1/(M,M,M)‐1interactions were much weaker than the homochiral (P,P,P)‐1/(P,P,P)‐1interactions. The results indicated that the propeller‐chiral (P/L)‐face interacts with the (P/L)‐face more strongly than with the (P/H)‐face, (M/L)‐face, and (M/H)‐face. The study showed the π‐face‐selective aggregation and π‐face chiral recognition of the configurationally stable propeller‐chiral molecules.