Construction of Chiral Nano-Space and Functionallization in Organic Zeolites based on Molecular Self-Assembly.

本课题以分子自组装为基础，在有机分子筛中构筑手性纳米空间和功能化为目的，开展了以下四个方面的研究。[1]具有不同氢键基团的六芳基苯及其多孔氢键网络的合成：我们通过二芳基乙炔的共催化环三聚反应制备了具有不同氢键基团以及功能基团的六芳基苯，作为有机沸石的支架。六（4-氨基甲酰基苯基）苯形成各种类型的三维氢键多孔网络，这取决于重结晶条件。[2]具有不同官能团的六（芳基乙炔基）苯的合成：我们以1，3，5-三溴-2，4，6-三碘苯为原料，通过双重Sonogashira偶联反应，制备了交替功能化的六（芳基乙炔基）苯。[3]具有手性基团的六（芳基乙炔基）苯的合成：我们通过第-2项中提到的反应制备了在1，3，5-位具有α-苯乙氧基作为手性基团并且在2，4，6-位具有4-羧基苯基1，4-吡啶基或4-氰基苯基作为用于网络形成的相互作用基团的六（芳基乙炔基）苯。我们将研究这些化合物对具有手性氢键或金属配位网络的手性有机沸石分子筛的功能。[4]含氨基酸的六芳基苯的合成：通过由第-1项反应制备的六（4-羧基苯基）苯或六（4-氨基苯基）苯与（L）-丙氨酸苄酯或N-Boc-（L）-丙氨酸的缩合反应，我们分别合成了具有C-或N-末端的六[4-（（L）-丙氨酸）苯基]苯。我们将研究这些化合物的功能，并将其导向具有手性氢键网络的手性有机沸石分子筛。

In this project, to the purpose for the construction of chiral nano-space and functionallization in organic zeolites based on molecular self-sssembly, we studied the following four items. [1]Synthesis of hexaarylbenzenes with various hydrogen bonding groups and their porous hydrogen-bonded network : We prepared hexaarylbenzenes with various hydrogen bonding groups as well as functional groups by the Co-catalyzed cyclotrimerization of diarylacetylenes, as a scaffold of organic zeolites. Hexakis(4-carbamoylphenyl)benzene forms various types of 3-D hydrogen-bonded porous networks, depending on recrystallization conditions. [2]Synthesis of hexa(arylethynyl)benzenes with various functional groups : We prepared alternately functionallized hexa(arylethynyl)benzenes by the double Sonogashira-coupling reactions using 1,3,5-tribromo-2,4,6-triiodobenzene. [3]Synthesis of hexa(arylethynyl)benzanes with chiral groups : We prepared hexa(arylethynyl)benzenes with α-Phenethyloxy group as a chiral group at 1,3,5-positions and with 4-carboxypheny1,4-Pyridyl, or 4-cyanophenyl groups as an interactive group for a network formation at 2,4,6-positions by the reaction mentioned in item-2. We will investigate the functions of these compounds directed towards chiral organic zeolites with chiral hydrogen-bonded o r metal-coordination network. [4]Synthesis of hexaarylbenzenes with amino acids : By the condensation reactions of hexakis(4-carboxyphenyl)benzene or hexakis(4-aminophenyl)benzene, which were prepared by the reaction of item-1, with (L)-alanine Benzyl ester or N-Boc-(L)-alanine, we synthesized hexakis[4-((L)-alanine)phenyl]benzenes with C-or N-terminals, respectively. We will investigate the functions of these compounds directed towards chiral organic zeolites with chiral hydrogen-bonded network.