Synthesis of New Highly-strained Cyclophanes Bridged by Cyclobutane Rings and Use of Their Properties

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A novel synthesis of cyclophanes using intramolecular [2 + 2] photocycloaddition of styrene derivatives was developed in our laboratories. So we were prompted to study its mechanism, its scope and limitation as a synthetic method, further reactions of cyclophanes obtained, and the use of properties of unique cyclophanes. Results obtained in the two year period of this project are listed below ; (1) Many vinylarenes, including 1, 3-bis (6-viny-1-1-phenanthryl) propance and cis-1, 2-bis (-vinyphenyl) cyclobutane, were prepared and irradiated. The corresponding phanes like a phenanthrenphane and [2.2] metacyclophane bridged by two cyclobutane rings were obtained. These results suggest the wide applicability of the reaction for cycrophane synthesis. (2) As one of mechanistic investigations, the effects of substituents attaching at the vinyl groups of vinylnaphthalene derivatives was studied. The reaction courses were affected greatly by the position and sort of substituents. (3) In order t … More o shorten the linkage by making a small ring, 1, 2-ethano [2.3] paracyclophane was brominated at the trimethylene chain, followed by the treatment with n-butyllithium, to afford the desired [2.2]paracyclophane linked by a cyclobutane ring and cyclopropane ring in a reasonable yield. This compound gathers much attention as one of the unique paddlaes. (4) cis-1, 2-Ethano-syn-[2.3] (1, 4) -naphthalenophane produced a highly strained cubane-type compound by photoirradiation. The product showed an interesting thermal cycloreversion, whose late was determined. (5) Small cyclophanes obtained by the reaction underwent the ring opening reaction. The rates of the reaction depended on the strain energies of the cyclophanes. (6) Cyclophanes obtained showed several intriguing properties like photochromism mentioned above, but there were no compounds which could be applied to any advanced materials. We would like to stress, however, that several crown ethers possessing cyclophane structures were prepared in surprisingly high yields and that did exhibit quite high Li^+ selectivity at the transport experiments. Less