以穿透後縮環方法合成車輪烷之研究

Abstract

第一部分： 合成車輪烷有許多策略可運用，如滑套法、夾鎖法、穿透後末端膨脹法、穿透後末端封鎖法以及穿透後縮環法。我們希望套用穿透後縮環法的合成概念：先以兩個啞鈴型分子穿透一個大環，在金屬離子引導之下縮環，形成無論是以有別於以往之合成方法或其別緻有趣含有兩個小環之造型[3]車輪烷。 第二部分： 當在溶劑中存在能互相辨識鍵結之主客分子時，其互相錯合生成的準車輪烷的比例受到幾個因素影響：如對應離子的鍵結強度、溶劑極性以及濃度的高低影響。若主客分子彼此的鍵結作用力弱，則須克服許多不利的因素，排除各種干擾鍵結的來源方能合成出車輪烷，研究弱鍵結生成的車輪烷之結構，並以此來探討其可能之應用。

Part I： Strategies for rotaxane synthesis such as “slippage”, “clipping”, “threading-followed-by-swelling”, “threading-followed-by-stoppering” and “threading-followed-by-shrinking” are reported. We hope to demonstrate that the “threading-followed-by-shrinking“ can also be achieved by metal-ion assisted through tandem reaction. Part II： The complexation of host and guest are influenced by the environment such as ion strength of counter-ion, polarity of solvent etc. We hoped to find suitable reaction to synthesize rotaxane in a weak hydrogen-bond system. A mild reaction was applied to interlock the macrocycle with the thread-like guest in the weak hydrogen-bond system to avoid possible interference accompanied by the reaction. Having this unique rotaxane in hand, we could study the bonding of the structure and discuss the application of the rotaxane.