洪偉修姚清發Wei-Hsiu, HungChing-Fa, Yao林宛諭Wan-yu, Lin2019-09-042017-6-302019-09-042012http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0696420325%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100707異噁唑及異噁唑啉類化合物於存在於自然界中，而由於其穩定的結構，使其可當作中間物且廣泛的應用在眾多的合成反應之中，而具有旋光性異噁唑及異噁唑啉類的化合物亦可應用於許多醫療治療中使用的藥物，因此合成具單一旋光性的化合物亦為研究合成的重要課題。 為了合成具旋光性的異噁唑及異噁唑類化合物，首先，本實驗使用硝基苯乙烯類化合物與炔丙基丙二酸二甲酯（或烯丙基丙二酸二甲酯），並添加具掌性的雙功能硫脲催化劑，利用其雙重活化的性質，可以與反應物有效鍵結，並控制其反應物之反應位向行1,4 Michael加成反應，提高反應的立體選擇性及鏡像選擇性，而合成出具有高產率及高鏡像選擇性的硝基烷化物。接著再利用鹼性試劑DBU (1,8-di- azabicycloundec-7-ene) 及脫水劑DFDNB(1,5-difluoro-2,4-dinitro- benzene)，在不破壞硝基烷化物的立體中心的條件下，行1,3-偶極環內加成反應，產生高鏡像選擇性的異噁唑及異噁唑啉類化合物。Isoxazole and isoxazoline derivatives are common and can be found in the nature compounds. The isoxazole derivatives structure are stable and facilitate for variety synthesis as intermediates. In medical system,enantiomeric isoxazole and isoxazoline are used in therapeutic process. Therefore, it becomes major tasks for synthesis enantiomeric isoxazole and isoxazoline. We have recently prepared nitrostyrene and dimethyl allyl malonate (and dimethyl propargyl malonate) with additive chiral bifunctional thiourea for 1,4-Michael addition. With H-bonding, the thiourea catalyst enhance the yield, stereo- and enantioselectivity of the reaction. At the next step, we use base reagent DBU (1,8-diazabicycloundec-7-ene) and dehydration reagent DFDNB (1,5-difluoro-2,4-dinitrobenzene) for synthesis of chiral isoxazole and isoxazoline. With 1,3-dipolar cycloaddition , we successfully synthesis high enantioselectivity isoxazole and isoxazoline.鏡像選擇性異噁唑有機催化劑硝基乙烯類麥可加成反應13-偶極環加成反應EnantioselectiveisoxazoleorganocatalystnitroolefinMichael reaction13-dipolar cycloaddition