在不對稱環化反應中硫偶極體常被當作碳原子的合成子，藉由硫偶極 體的親核基加成到具有親電性的起始物上進行環氧化合物、氮丙啶化合物 以及環丙烷化合物的合成。論文中使用實驗室所發表以及開發的掌性硫化 物，將此掌性硫化物應用在過渡金屬的不對稱 [4+1] 環化反應中，希望能 開發出更多的應用性。 在大自然中許多具有生物活性的?類化合物都是經由酵素對異戊二烯 類的化合物進行環化反應。而此多烯環化的反應一直被認為是合成具有生 物活性的?類化合物和其他天然物的重要反應，藉由多烯環化的反應能夠 有效的將分子中的碳進行鍵結同時控制其立體結構。受到 William R. Dichtel’s 的研究所啟發，我們使用 1,1′-聯-2-?酚為基底的單體與三烯化合 物作為架橋分子，利用環合置換反應將兩種化合物進行鍵結合成出掌性共 價有機框架材料，將其應用在多烯環化反應中並且探討異相催化劑在多烯 環化的應用及發展性。;Sulfur ylides have long been used as one-carbon synthons in many kinds of transformations, such as synthesis of epoxides, aziridines, and cyclopropanes through ylide addition to the electron-poor π system. Our lab has previously reported the enantioselective synthesis of (S)-thionyl diphenylmethanol and the application of its benzyl ether derivative in asymmetric synthesis, catalytic CoreyChaykovsky reaction of benzyl bromide, and aldehydes to give trans-epoxides in high yield with good to high enantiomeric excess. The ability of sulfur-based ylides to efficiently participate in transition metal-catalyzed [4+1] cycloaddition was found recently. Further extension of the application of this chiral sulfide to participate in transition metal-catalyzed [n+1] cycloaddition is explored by using our catalyst (THTOBn) or its sulfonium salt in this thesis. A variety of terpenoids are enzymatically synthesized by cyclization of polyprenoids such as squalene, farnesol, geranylgeraniol in the biological system. Polyene cyclization is recognized as a unique and efficient way to build structural complexity from acyclic molecules via concerted and stereo-controlled C–C bond formations. In this work, we use a new type of porous material, chiral covalent organic frameworks (CCOFs) as a chiral source and catalyst to conduct polyene cyclization. Inspired by William R. Dichtel’s work, we plan to adopt ring-closing metathesis strategy for the construction of CCOFs from 1,1′-Bi-2-naphthol (BINOL) type monomers and triene linkers.
