合成車輪烷的新方法及其應用

The Mild and Efficient Method of Rotaxane Syntheses and Its Applications

洪偉崇(Wei-Chung Hung)

指導教授 ： 邱勝賢

國立臺灣大學/理學院/化學研究所/碩士(2005年)

https://doi.org/10.6342/NTU.2005.01429

摘要

我們發現benzylic azides與trialkyl phosphite作用形成dialkyl phosphoramidate的反應，可相當有效率地被應用於不同孔徑的大環分子與dibenzylammonium ion (DBA+) 之辨識系統，來合成[2]車輪烷分子。若以二十四員環之dibenzo-[24]crown-8 (DB24C8)，或是與DBA+之錯合能力相當弱的di(p-toluidine)[24]crown-8 (DPT24C8)，則diethyl phosphoramidate可作為適當之封鎖基；若大環分子為二十六員環，則須以dibutyl phosphoramidate作為封鎖基。
我們亦合成一個具有雙重辨識單元的大環分子，不但可與DBA+錯合，更可利用鈀(II)離子之四配位特性，連接大環分子與吡啶衍生物，以形成準車輪烷的結構。我們分別利用這兩種辨識單元，合成出對應的[2]車輪烷分子。

關鍵字

超分子化學 ； 車輪烷

並列摘要

The mild and efficient reaction between trialkyl phosphite and benzylic azides allows us to construct rotaxanes utilizing the recognition motif of macrocycles, with different sizes, and dibenzylammonium ion (DBA+). In the case of 24-membered macrocycles, such as dibenzo[24]crown-8 (DB24C8) and di(p-toluidine)[24]crown-8, which binds DBA+ ions much more weakly than does DB24C8, diethyl phosphoramidate is a suitable stopper. For 26-membered macrocycle, the larger dibutyl phosphoramidate is needed to act as a stopper.
The dual-use macrocycle, which owns double recognition motif was also synthesized. Not only complexing with DBA+, it also attached with the derivatives of pyridine via Pd(II). Applying both recognition motifs, rotaxanes are successfully synthesized respectively.

並列關鍵字

supramolecular chemistry ； rotaxane

參考文獻

33.Cheng, P. N.; Hung, W. C.; Chiu, S. H. Tetrahedron Lett. 2005, 46, 4239-4242.

6.(a) Collin, J.-P.; Dietrich-Buchecker, C.; Gavina, P.; Jimenez-Molero, M. C.; Sauvage, J.-P. Acc. Chem. Res. 2001, 34, 477-487. (b) Leigh, D. A.; Wong, J. K. Y.; Dehez, F.; Zerbetto, F. Nature 2003, 424, 174-179. (c) Badjic, J. D.; Balzani, V.; Credi, A.; Silvi, S.; Stoddart, J. F. Science 2004, 303, 1845-1849.

8.(a) Molecular Electronics: Science and Technology; Aviram, A., Ratner, M., Eds.; New York Academy of Sciences: New York, 1998. (b) Collier, C. P.; Mattersteig, G.; Wong, E. W.; Luo, Y.; Beverly, K.; Sampaio, J.; Raymo, F. M.; Stoddart, J. F.; Heath, J. R. Science 2000, 289, 1172- 1175. (c) Yu, H.; Luo, Y.; Beverly, K.; Stoddart, J. F.; Tseng, H.-R.; Health, J. R. Angew. Chem., Int. Ed. 2003, 42, 5706-5711

3.Wasserman, E. J. Am. Chem. Soc. 1960, 82, 4433.

4.Harrison, I. T.; Harrison, S. J. Am. Chem. Soc. 1967, 89, 5723.