Alteration of Organic Synthetic Processes Using Organic Zeolites in Water

我们研究了基于蒽-双间苯二酚衍生物的“有机沸石”的微孔速度、客体结合特性和催化行为。主要研究成果如下：(1)含镧有机沸石通过烯醇类中间体催化羰基底物的各种反应。然而，对于酮与CO_2的羰基化和糖的异构化等反应来说，情况并非如此，在这些反应中，螯合型产物与金属中心显示出很强的亲和力，以阻止催化剂的循环。(2)三苯基膦的镧配合物被用于网络各种重金属，如Pd(II)、Ru(II)、Rh(II)和Pt(II)，以获得微孔材料。它们能够促进这些金属的特征反应，如。但仅以化学计量方式偶联；这是因为还原的金属中心的再氧化仍然是一个问题。(3)吖啶-双间苯二酚衍生物是一种“自互补”的构建块，其中氮充当间苯二酚部分的一种“客体”，以提供配位饱和和坚固的微孔材料。作为客体的苯可以在不显著改变晶体结构的情况下被脱除。(4)蒽-双(异磷酸)形成了一个非常健壮的氢键网络，能够对甲烷进行可逆的吸附-脱附。揭示了真正的小孔动物的晶体结构。(5)还尝试利用糖簇作为有机沸石在水中稳定的来源。以杯[4]间苯二烯为基础的大环糖簇以一种大小和数量可控的方式包裹质粒DNA，得到大小为50纳米的人造“糖病毒”。

We investigated the microporocity, guest-binding properties, and catalytic behaviors of "organic zeolites" based on anthracene-bisresorcinol derivatives. The major achievements are as follows.(1) Lanthanum-containing organic zeolites catalyze various reactions of carbonyl substrates which proceed via enolate intermediates. This is, however, not the case for such reactions as carbonylation of ketones with CO_2 and isomerization of sugars, in which the chelate-type products show strong affinity to the metallic center to prohibit turnover of the catalysts.(2) Lanthanum complexes of triphenylphosphine was used to network various, heavy metals such as Pd(II), Ru(II), Rh(II), and Pt(II) to give microporous materials. They are capable of promoting, characteristic reactions of these metals such as. coupling but only in a stoichiometric manner ; this is because reoxidation of reduced, metal centers is still a problem.(3) Acridine-bisresorcinol derivatives serve as a "self-complementary" building blocks in which the nitrogen acts as a kind of "guest" for the resorcinol moiety to give coordinatively saturated and robust microporous material. Benzene as a guest can be removed without changing the crystal structure significantly.(4) Anthracene-bis(isophtalic acid) gives rise to a remarkably robust H-bonded network capable to reversible adsorption-desorption of methane. The crystal structure of genuine microporopus crystal structure was revealed.(5) Attempts were also made to utilize glycoclusters as a source of organic zeolites stable in water. The calix[4]resorcarene-based macrocyclic glycoclusters encapsulate plasmid DNA in a size-and number-controlled manner to give artificial "glycovirus" of a size of 50 nm.