I. 經有機膦催化誘導4-亞芳基吡唑酮和5-亞芳基噻唑酮的β-醯化反應II. 鹼催化2-羥基亞胺葉立德與2-羥基亞芳基噻唑酮經由1,3-偶極體環化/分子內環化反應合成螺環𠳭酮[3,4-b]吡咯啶

Abstract

第一部分：敘述實驗室設計使用α,β-不飽和共振系統的4-亞芳基吡唑酮和5-亞芳基噻唑酮以一鍋化反應中藉由非金屬有機膦催化反應對β位置進行親核共軛加成，接著藉由氧醯化/分子內環化反應形成中間體Phosphrous betaine 接著經由分子內重排反應，最終可以得到具有立體專一性並且產率高達90%以上β-碳醯化反應4-亞芳基吡唑酮以及5-亞芳基噻唑酮的產物。第二部分：經由設計開發出一種經由2-羥基亞胺葉立德與2-羥基亞芳基噻唑酮透過有機鹼催化反應1,3-偶極體環化加成反應以及進一步的連鎖反應建構出螺環𠳭酮[3,4-b]吡咯啶的方法，而最佳化結果顯示，可以在短時間內得到高達93％的產率。另外我們實驗室正在努力設計出不同取代基效應的螺環𠳭酮[3,4-b]吡咯啶以及不對稱合成的研究。I. An efficient phosphine-catalyzed Beta-C-acylation methodology of pyrazolones and thiazolones arylidene were reported in thesis. Various bata acylated products were affordrd from the corresponding 4-arylidene pyrazolones and 5-arylidene thiazolones with acyl chlorides under organophosphane catalysis, resulting in excellent yields and specific stereoisomers. The reaction is believed to proceed via a tandem phospha-Michael addition/O-acylation/intramolecular betaine formation/acyl group rearrangement sequence. Furthermore, this methodology can also be applied in gram-scale with similar efficacy.II. An organobase-catalyzed diastereoselective synthesis of thiazolone spirochromeno[3,4-b]pyrrolidine were reported in the part II of this thesis. The optimized method provided the desired spirochromeno[3,4-b]pyrrolidines in good yield from the cascade 1,3-dipolar cycloaddition/lactonization of 2-hydroxyl azomethine ylide and 2-hydroxyarylidene thiazolone in a short reaction time.