發(fā)布時間：2018-03-15 10:09

  本文選題：拆分　切入點：二酮　出處：《中國科學技術大學》2017年博士論文　論文類型：學位論文

【摘要】：本文主要分為兩章,分別研究了:對2,3:6,7-二苯并二環(huán)[3.3.1]-2,6-庚烯-4,8-二酮的拆分和對倍半萜Aquatolide的全合成。第一章是高效地拆分2,3:6,7-二苯并二環(huán)[3.3.1]-2,6-庚烯-4,8-二酮化合物并對其進行衍生化的研究。本章通過手性1,1'-聯(lián)-2-萘酚直接對上述二酮進行拆分,而且成功得到了拆分中間體的單晶結構,通過X射線單晶衍射,觀測到1,1'-聯(lián)-2-萘酚羥基氫與酮羰基之間的氫鍵相互作用,并且確定了產(chǎn)物的絕對構型。這種拆分方法高效且實用,可以放大到克級的規(guī)模,通過一次拆分就能以大于85%的總產(chǎn)率和大于99%的ee值得到上述手性二酮,而且手性1,1'-聯(lián)-2-萘酚還可以以大于95%的產(chǎn)率回收,其ee值也沒有發(fā)生任何變化。我們還對上述二酮進行衍生化研究,合成了幾種手性醇和手性胺類化合物。第二章是對倍半萜Aquatolide的全合成。從環(huán)戊二烯基鈉出發(fā),通過25步反應完成了對Aquatolide的全合成。首先采用一種較為溫和的方法構建重氮化合物,然后通過沃爾夫重排反應,以一種比較高效的方法構建了具有較大張力的四元環(huán)結構。對于八元環(huán)的合成,我們設計了兩條合成路線:第一條路線中,嘗試通過分子內(nèi)的醛對炔烴進行加成來構建八元環(huán)結構,但我們沒有得到產(chǎn)物;第二條路線是基于Z式三取代的碘代烯烴,通過Nozaki-Hiyama-Kishi反應構建最后一個八元環(huán)骨架,然后經(jīng)過斯文氧化合成了倍半萜Aquatolide。
[Abstract]:This paper is divided into two chapters. The resolution of [3.3.1] -2o 6-heptene-4-octene-8-dione and the total synthesis of p-sesquiterpene Aquatolide were studied respectively. The first chapter is about the efficient resolution and derivation of 2 ~ (3: 3): 6 ~ (7) -dibenzobicyclo [3.3.1] -26-heptene-4N ~ (8-dione). The above mentioned diketones are directly resolved by chiral 1H 1C-BIS-2-naphthol, The single crystal structure of the intermediate was successfully obtained. The hydrogen bond interaction between hydroxyl hydrogen and ketone carbonyl group was observed by X-ray single crystal diffraction. And the absolute configuration of the product is determined. The method is efficient and practical, and can be enlarged to the scale of gram class. By one resolution, the chiral diketone can be obtained at a total yield of more than 85% and ee greater than 99%. Moreover, the chiral 1H 1C Bis 2 naphthol can be recovered in a yield greater than 95%, and its ee value has not changed in any way. We have also studied the derivatization of the above mentioned diketones. Several chiral alcohols and chiral amines have been synthesized. Chapter 2 is the total synthesis of p-sesquiterpene Aquatolide. The total synthesis of Aquatolide was completed in 25 steps. First, a mild method was used to construct diazo compounds, and then through the Wolff rearrangement reaction, A quaternary ring structure with high tension is constructed by a more efficient method. For the synthesis of octa-ring, we have designed two synthetic routes: in the first route, An attempt was made to construct an octa-ring structure by the addition of intramolecular aldehydes to alkynes, but we did not get the product. The second route was based on the Z-type tri-substituted iodinated alkenes, and the last octa-ring skeleton was constructed by Nozaki-Hiyama-Kishi reaction. Then the sesquiterpene Aquatolide was synthesized by Sven oxidation.
【學位授予單位】：中國科學技術大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O622
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本文編號：1615563