Studies on Molecular Design of Condensed Heterocycles Directed Toward Functional Materials

本项目开发了含有吡啶和/或吡咯骨架的稠合杂环化合物的分子设计的新方法。此外，还建立了多种稠合杂环化合物功能化的新方法。这些过程不仅被概括和简化，而且通过对产物的结构-功能相关性的评估，使得这些过程变得高效和精确。作为这类化合物的功能之一，氮杂环类化合物具有很强的杀菌活性，其与电离势的相关性被揭示出来。此外，还合成了含有稠合杂环的齐聚物和聚合物，并将其应用于功能染料、聚合物杀生剂、非线性光学等领域。另一方面，开发了多种合成路线，设计了新型辅酶PQQ和TTQ模型，阐明了生化催化氧化还原过程的机理。基于这些结果，成功地设计出了更有效的具有更高催化活性的辅酶模型。该项目的另一个特点是有效地利用分子力学计算和分子轨道计算来分析分子结构和反应路径，从而更好地进行杂环的分子设计。作为系统研究的结果，我们可以阐明杂原子的种类、数量和位置、环的大小和组合以及取代基对稠合杂环作为功能材料的各种性质的影响。这些相关性和新建立的方法将直接有助于天然产品、功能材料、生物活性物质等的分子设计。

Novel methodologies for molecular design of condensed heterocyclic compounds containing pyridine and/or pyrrole skeletons have been developed in this project. A variety of novel methods for functionalization of condensed heterocyclic compounds were also established. These processes were not only generalized and simplified, but also made highly effective and precise through assessment of structure-function correlation of the products.As one of functions of these types of compounds, azaindoles showed strong germicidal activity whose correlation with ionization potential was unveiled. Oligomers and polymers containing condensed heterocycles were also synthesized and applied to functional dyes, polymeric biocides, nonlinear optics and so on.On the other hand, a number of synthetic routes were developed to design models of novel coenzymes, PQQ and TTQ, which clarified the mechanisms of biochemical catalytic oxidation-reduction processes. Based on these results, more effective design of coenzyme models having superior ctalytic activity was successful. Another feature of this project is that molecular mechanical calculations and molecular orbital calculations were efficiently utilized to analyze molecular structures and reaction pathways which enabled better molecular design of heterocycles.As the results of the systematic investigation, we could clarify effects of sort, number and position of heteroatoms, size and combination of rings, and substituted groups on various properties of condensed heterocycles as functional materials. These correlations and newly established methodologies will directly contribute to molecular design of natural products, functional materials, biologically active substances, etc.