(1) 合成抗反轉錄病毒藥物之中間體反應探討 (2)開洞富勒烯之性質探討

Abstract

gamma-內醯胺所衍生的抗HIV化合物已經在許多文獻上被發表出來，如以Amprenavir和Indinavir為基礎所做出的gamma-內醯胺化合物，都成功的與蛋白酶結合而抑制其作用，因為合成出此類化合物的起始物就為gamma-內醯胺，所以發展出合成gamma-內醯胺的化合物，使有利於進行下一步的合成。利用三級膦的化合物與稀炔和亞胺進行一鍋化的反應，三級膦會優先攻打三鍵上的alpha位，之後進行環化反應，形成gamma-內醯胺的化合物，經過氫譜、碳譜、磷譜、紅外線光譜、質譜和單晶繞射的鑑定，則可驗證出此結構帶有Ylide結構，並在藉由三級膦與雙炔和醛類的反應更加證明此反應機構的推導。因為此產物帶有Ylide結構，所以可以進行Wittig反應，在日後全合成上必有一些幫助。 另一方面，利用碳七十對其開洞到20員環的過程，來探討跟碳六十開洞一些不一樣的地方，並藉由12員環異構物的單晶繞射來探討其機構，之後將碳七十擴環到20員環，利用變溫NMR實驗來看洞裡的含水量有何變化，並藉由紫外可見光光譜和循環伏安法計算出碳七十20員環的HOMO和LUMO，並與PCBM和ICBA做比較。

Antiretroviral drug have been developed in recent years and some antiretroviral drugs are commercial available. For example, Amprenavir and Indinavir are some of these commercial available drugs. Issues of some side effects and the cost for production of these antiretroviral drug have been primary concerns. Highly-efficient and low-cost synthetic procedures for drug syntheses can be conducive to human. Some gamma-lactam antiretroviral drugs have been reported, such as gamma-lactam-like Amprenavir and Indinavir. Because these drugs are gamma-lactam derivatives, we are interested in developing a one-pot synthetic method to its synthetic precursors. In this study, we used phosphine, (E)-dimethyl hex-2-en-4-ynedioate and N-Benzylidene-p-toluenesulfonamide to obtain the gamma-lactam intermediates bearing ylide functionality. We characterized these products by 1H, 13C, 31P, IR, Mass and X-ray diffraction analyses. These readily available structures may be adventageous to the total synthesis of molecules having lactam moiety. The other study, we synthesized the 12-member ring of [70]fullerene and we also studied the isomers about the open-cage products. Form the reference of Iwamatsu, we can use 1,2-Diaminobenzene to enlarge 12-member ring of [70]fullerene to 20-member ring. We can find the water in the 20-member ring product by 1H NMR. Because water can go inside the 20-member ring spontaneous, we did the variable temperature NMR experiment to see that the ratio of water inside when change the temperature. Finally, we characterized the HOMO, LUMO and band gap of 20-member ring and compare with the PCBM and ICBA.