【作者】 刘锋；

【导师】 张俊良；

【作者基本信息】 华东师范大学 ， 有机化学， 2009， 硕士

【摘要】 多取代的呋喃化合物存在于许多天然产物当中,而且也应用于医药,植物生长调节剂,食品添加剂,印染等领域中。同时在合成化学中,也是合成复杂的天然产物或非天然产物的重要合成中间体,因此对它们的合成和转化的研究一直是有机化学方法学研究的热点。近年来,金（Au）作为一种强的Lewis酸在催化反应中的应用已经成为了一个研究热点,其对不饱和键的活化能力也被化学家们认识。本论文是关于共轭烯炔酮与硝酮化合物反应生成多取代的呋喃化合物的研究,主要从三个方面进行了研究。1.共轭烯炔酮与硝酮的高非对映选择性的反应我们从3-（1-苯乙炔基）-4-苯基-3-丁烯酮与硝酮反应出发,发现在PPh₃AuCl/AgOTf的催化下发生了[3+3]的反应且形成了双并杂环化合物,而且在PPh₃AuCl/AgOTf催化下反应得到了高非对映选择性的产物。2.产物的转化双并杂环化合物产物与二碘化钐或硝酸铈铵反应可以化学选择性地打开其中的一个杂环,从而分别得到了噁嗪类化合物和含有氨基和羟基的四取代呋喃类化合物。3.联苯类手性磷配体的合成及其在共轭烯炔酮与硝酮反应中的应用由间溴苯甲醚出发合成了三种联苯类的手性磷配体,应用到了共轭烯炔酮与硝酮的反应当中,并且得到很高的的ee值。更多还原

【Abstract】 Highly substituted furans can be found as core structure in many natural products,commercially important pharmaceutical,food taste enhancers,bioregulators and dynes.In synthetic chemistry,it is also considered as a kind of synthetic intermediate for the construction of numerous cyclic and acyclic compounds.Many chemists focused their research interests on the development of new methodologies for the synthesis and transformation of this kind of compounds.Gold complexes known as a kind of powerful Lewis acid,has extensively studied in catalytic reactions in past decade.For example,they can readily activate alkynes, allenes and olefins to react with a variety of nucleophiles.In this thesis,we have focused on the synthesis of highly substituted furan by the cycloaddition reaction of conjugated enynones with nitrones.This thesis includes the following three parts:PartⅠ:High diastereoselective cycloaddition reaction of conjugated enynones with nitrones.Under the catalysis of Ph₃PAuOTf,we found that the reaction of 2-（phenylethynyl）cyclohex-2-enone with（Z）-N-benzylideneaniline oxide（nitrone） can give a novel heterobicyclic product with high regioselectivity and diastereoselectivity.PartⅡ:Transformation of productsThe products were treated with SmI₂ or cerium（Ⅳ） ammonium nitrate（CAN） could give oxazine and highly substituted furan compounds,respectively,in good yields by a chemoselective ring opening.PartⅢ:Synthesis and application of chiral biphenyl type phosphorus ligandsThree chiral ligands,Such as（R）-MeO-BIPHEP,（R）-C1TunaPhos and （R）-C3TunaPhos have been synthesized from m-bromoanisole according to reference’s procedure.We are pleased to find that（R）-C1TunaPhos can give the best ee value.更多还原