一、(+)-Antrocin的全合成研究 二、n-型有機場效電晶體:硫化苝雙亞醯胺合成及研究 三、四氫異喹?噻唑烷之連鎖加成反應研究

I. Total Synthesis of (+)-Antrocin II. Study and Synthesis of Thionated Perylene Diimides for n-Channel Organic Field Effect Transistors. III. Thiazo[2,3-a]tetrahydroisoquinolines from Addition Reaction of 3,4-Dihydroisoquinolines with (E)-4-Mercapto-2-butenoic Ester.

黃聖涵(Sheng-Han Huang)

指導教授 ： 楊德芳 ； 李瑜章 ； 卓重光

國立暨南國際大學/科技學院/應用化學學系/博士(2017年)

摘要

本論文分為三個研究部份。第一部份為(+)-Antrocin的全合成，藉由合成(+)-Antrocin來釐清天然物(-)-Antrocin的絕對立體結構，在本合成路徑中，關鍵步驟分別以樟腦烷酯類三烯衍生物進行分子內Diels-Alder反應時具有不錯的產率和立體選擇性，利用不同的催化劑有效的控制氫化反應的產物。接著利用理論計算，瞭解分子內Diels-Alder反應機構之進行和提出合理的反應機構。最後整個合成路徑以市售的2,2-dimethyl cyclohexanone為起始物進行15個步驟合成到(+)-Antrocin總產率為7.3%。
第二部份為我們設計和合成一系列新的n型有機場效電晶體硫化苝雙亞醯胺化合物，這類型的硫化苝雙亞醯胺化合物可以利用市4-溴-1,8-萘酐為起始物經由5個步驟及可完成合成。接著、由光化學和電化學中發現這類硫化苝雙亞醯胺化合物具有特別的電、光化學性質，相較於其他苝雙亞醯胺衍生物，我們發現硫化反應得到的硫化苝雙亞醯胺化合物可以有效的降低最低未占分子軌域 (LUMO)和縮小能階的差距。
第三部份為我們開發更環保和有效的方式來合成四氫異喹?噻唑烷衍生物，以四氫異喹?和α,β-不飽和酯類為起始物，進行連鎖Michael / 親核性加成反應。這一系列反應的優點分別為環保的溶劑、不用使用任何催化劑和配體、符合原子經濟學、進行各種不同的取代基的測試以及整體產率為60-83%。

關鍵字

全合成 ； 硫化苝雙亞醯胺化合物 ； 四氫異喹?噻唑烷衍生物

並列摘要

Part 1: This thesis three parts. The frist total synthesis of (+)-antrocin, which was need to clarify the absolute structure of the natural sesquiterpenoid (-)-antrocin. Special transformations in this synthetic route include highly stereoselective intramolecular Diels-Alder reaction (IMDA) of camphanate triene intermediate and highly efficient selective hydrogenation with two different catalysts. We explain the key intramolecular Diels-Alder reaction mechanism by density functional theory calculation. Overall the (+)-anrtocin was synthesized starting from commercial available 2,2-dimethyl cyclohexanone in 15 steps and the total yield was 7.3 %.
Part 2: We designed and synthesized a new series of thionated perylene diimides (PDTI), which could be used for N-channel organic field effect transistor. The PDTI were synthesized in the five steps strating from commercial available 4-Bromo-1,8-naphthalic Anhydride. Electrochemical and photophysical properties of PDTI were different and special from Perylene Diimide analogs. Significantly, the thionated compounds had narrower energy gaps and lower lowest unoccupied molecular orbital (LUMO) levels than those of their corresponding imide analogs.
Part 3: A green and highly efficient method for the building of a variety of thiazo[2,3,-a]tetrahydroiso quinolines by tandem addition [Micheal / nucleophilic addition] of 3,4-dihydro- isoquinolines with (E)-4-mercapto-2-butenoic ester in green solvent. The adventages of using environmental friendly solvent, catalyst-free, ligand-free, atom-ecomonic,and having wide functional group are described. The yields of thiazo[2,3,-a]tetrahydroisoquinolines ranged from 60% to 83%..

並列關鍵字

total synthesis ； thionated perylene diimides ； thiazo[2,3,-a]tetrahydroiso quinolines

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