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”的微孔隙度、客体结合性能和催化行为。主要成就如下。(1)含镧有机沸石催化羰基底物的各种反应，这些反应通过烯醇酸中间体进行。然而，在酮与CO_2羰基化反应和糖异构化反应中，螯合型产物对金属中心有很强的亲和力，从而阻止催化剂的翻转。(2)利用三苯基膦的镧配合物网状各种重金属，如Pd（II）、Ru（II）、Rh（II）和Pt(II)，得到微孔材料。它们能够促进这些金属的特征反应，如。偶联，但仅以化学计量的方式；这是因为再氧化还原，金属中心仍然是一个问题。(3)吖啶-双间苯二酚衍生物是一种“自互补”的结构单元，其中氮作为间苯二酚部分的“客体”，形成协调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去除。(4)蒽-双（异戊酸）产生了一个非常强大的h键网络，能够可逆地吸附-解吸甲烷。揭示了真实微孔藻的晶体结构。(5)还尝试利用糖团簇作为在水中稳定的有机沸石的来源。以杯形[4]间苯carene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，以获得50纳米大小的人工“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.