1. Total Synthesis of (+)-Antrocin 2. Study and Synthesis of Thionated Perylene Diimides for N-Channel Organic Field Effect Transistors3. Thiazo[2,3-a]tetrahydroisoquinolines from Addition Reaction of 3,4-Dihydroisoquinolines with (E)-4-Mercapto-2-butenoic Ester.

• Main Authors: Huang, Sheng-Han, 黃聖涵
• Other Authors: Yang, Te-Fang
• Format: Others
• Language: zh-TW
• Published: 2017
• Online Access: http://ndltd.ncl.edu.tw/handle/05116601965888128991

博士 === 國立暨南國際大學 === 應用化學系 === 105 === 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]tetrahydroisoquinolines 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%.