Alteration of Organic Synthetic Processes Using Organic Zeolites in Water

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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.