Studies on Synthesis, Reaction and Functionality of the Bridged Aromatic Compounds

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1. The development of synthesis of the bridged aromatic compounds Although there are numerous reports concerning synthesis of the bridged aromatic compounds, their preparative routes seem to be too long for practical purposes. The [2.2]meta- and [2.2]metaparacyclophanes are so highly strained compounds that may be reactive toward many reagents. However, the chemistry of these compounds is very limited since their preparation from easily available compounds are very limited. In this work, we have developed the convenient preparation of the strained bridged aromatic compounds using the tert-butyl function as a positional protecting group on aromatic ring. Furthermore, we have applied this method to the synthesis of large membered macrocyclic metacyclophanes.2. Relationship between the reactivity and structures. Electrophilic substitution reactions of medium-sized cyclophanes were studied in order to investigate the relationship between the reactivity and the molecular strain. For example, in the electrophilic aromatic substitution of 8-substituted [2.2]metaparacyclophanes the isomerization and tramsannular reaction due to the release of the molecular strain were observed. We have studied on the reactive organic intermediates, which are contained cyclophane skeleton, for example, carbenes, nitrenes, and benzaynes etc.3. The development to the advanced materials. The conformational studies of cyclophanes and the application for the advanced materials, for example photo-response materials, host compounds, and new conductive cyclophane polymers etc. were investigated. For example, the functionalized macrocyclic metacyclophanes, which we have designed in this work found to act as host compounds and have abilities of molecular recognition such as organic compounds and metal ions.The relationship between the reactivity and physical properties was also investigated by X-ray diffraction analysis.