手性Brφnsted酸催化含氟α-氨基膦酸酯的不对称合成及生物活性应用研究.pdf

贵州大学硕士学位论文手性Brφnsted酸催化含氟α-氨基膦酸酯的不对称合成及生物活性研究姓名:张玉平申请学位级别:硕士专业:农药学指导教师:Pinaki ;宋宝安 20080501 资州人学2008扁顾I:,具有许多重要的生物活性,例如: 除草、杀菌、植物生长调节、抗癌和抗病毒作用。相关研究发现,。l,超着重爱作粥,。为了寻找高效、低毒、环境友好舱抗烟草花叶病毒制刹,本文以手憔联二萘酚(BINOL)为原料,在无水无氧的条件下,经甲基化、硼酸化、Suzuki偶联、还雁、酯化等五步反赢,合成手性Bronsted酸:《灭).3,3’.双《3,).1,l’一联二萘酚膦酸酯,以其作催化剂,催化底物亚胺与亚磷酸酯的加成,设计并合成了14个泰见文献报道的有较高光学活性的N。, 通过R、1H NMR、"C NMR、31P NMR、”F NMR、元素分析对目标化合物进行了结构表征,并膈HPLC进行光学活性测定,匿标物的光学活性ee:。6%; 同时,对催化剂和I}标物的合成办;矢、反应条件等进行了优化。采用半时桔斑法对所合成的化合物进行了抗烟草花哪。病毒(TMV)活性测定, 测试结果表明:此炎化合物n:500¨∥mL i:6c,叟下对烟草花叶病毒均有一定的抑制豫用;其中纯合物29的抗秘V活体治疗活性为52。20%,接近予对照药剂宁南霉素(%);%:2a、29、%、 80。21%、%f该测试纂件下,宁南霉素的活体保护、钝化的搠割率分别为 %,%)。关键词:手I!E含搬“.氰J是瞵簸帕: Bronsted敝催化剂;刁i财称合成: 抗潮尊花l||.瘸,{iiir,-fl-: 图书分类号:062 +4 2 贵州人学2008膈坝I:研究生L#业论文 Abstract acids,bioisoters ofnatural amine acids,have been found to exhibit a wide range of biological a-aminophosphonic acid derivatives are used as herbicides,fungicides,plant growth regulators,anti—cancer agents andhave stereochemistry atthea_carbon atom plays allimportant roleinthebiological activity ofthemolecule,the synthesis ofchiral has been afocus of considerable attention anic chemistry,pesticidechemistry aswell asinmodem pharmaceutical chemistry. Keeping these considerations inmind,in order tofindpotent environmental friendly and non toxicantiviralagents against o mosaic virus《TMV),fourteen new fluorine containing bioactive chirala—aminophosphonates inhi【gh enantiomeric purity were asymmetrically synthesized using chiralBronsted anocatalyst derived from(尺).binaphthol(BINOL)in atypical hydrophosphonylation reaction of aldimines obtained from cinnamaldehyde and fluorinated aromatic amine withdialkyl synthetic methods and optimization of reaction conditions are discussed in thethesi