- 學位論文
(I)結合田丸丙烯基化/烯烴複分解反應之(±)-圆錐定 C和2-甲基咔唑全合成及(II)藉由α-氰基-β-炔基羰基衍生物的溫控硫化來合成2-氨基噻吩和噻吩[2,3-c] 并異噻唑
(I)A Combined Tamaru Allylation/Olefin Cross-Metathesis Approach for the Total Syntheses of (±)-Paniculidine C and 2-Methylcarbazole and (II)Temperature-Controlled Thiation of α-Cyano-β-Alkynyl Carbonyl Derivatives for De Novo Synthesis of 2-Aminothiophenes and Thieno[2,3-c]isothiazoles
摘要
此論文分為兩個章節； 第一章主要描述利用市售的吲哚來合成2-甲基咔唑，其經由一連串的田丸丙烯基化、烯烴複分解反應和自動氧化傅-克環化反應生成，而此篇實驗代表著3-戊稀吲哚和2-甲基咔唑生物鹼之間的確可能具有生物合成關聯，此外，我們還探討3-烯丙基吲哚和各種受保護的烯丙醇之間烯烴複分解反應的優化。 第二章節則是敘述新穎的方法學，藉由容易獲得的炔基腈來快速合成2-氨基噻吩和噻吩[2,3-c] 并異噻唑，此轉化是利用五硫化二磷與Lawesson試劑的溫控硫化反應完成，並且我們透過分離的中間產物來推導合理的反應機構，我們更進一步的探索此方法學，合成一系列不同官能基的含硫雜環。
並列摘要
This dissertation is divided into two parts: The first chapter describes the synthesis of 2-methylcarbazole from the commercial available indole through a series of reactions comprising a Tamaru allylation, an olefin cross metathesis and an auto-oxidative Friedel-Crafts cyclization. This experiment suggests a possible biosynthetic link between 3-prenylated indoles and 2-methylcarbazole alkaloids. Moreover, we explored the optimization of cross metathesis reactions between 3-allylindole and various protected allyl alcohols. The second chapter describes a novel methodology for the facile synthesis of 2-aminothiophenes and thieno[2,3-c]isothiazoles from readily available alkynyl nitriles. These transformations take advantage of temperature-controlled thiation reactions with phosphorous pentasulfide and/or Lawesson’s reagent. A plausible mechanism was delineated based on the analysis of isolated intermediates, especially a ketothioamide. The protocol has been further explored for preparing a series of sulfur-containing heterocycles with different functional groups.