(一)、亞芳基吡唑哢與亞芳基二氫茚二酮插烯-麥可串級反應：利用有機不對稱催化劑建構出具有鏡像選擇性的五個或四個四級碳立體中心的複雜(籠狀)骨架(二)、利用亞磷酸鹽或膦酸酯合成茚並呋喃酮衍生物

Abstract

在本實驗室過去的兩篇報導中使用有機不對稱試劑進行複雜的串級反應可有效地建構五個四級立體中心。本篇以5-甲基亞芳基吡唑哢衍生物作為親核試劑，經動態光學分割和不對稱插烯麥可加成至亞芳基二氫茚二酮衍生物上，隨後經縮醛/氧雜麥可/麥可串級反應，成功地建構出有良好的產率和鏡像選擇性的複雜籠狀骨架。當5-芳基亞芳基吡唑哢衍生物作為親核試劑進行插烯麥可加成/互變異構化後，再經過關鍵的質子轉移步驟和羥醛加成/縮醛化反應，成功地構建具有連續5/5/6環之螺環吡唑哢產物。本反應在不對稱多樣性導向合成的研究方面具有潛力。藉由使用不同種類的膦試劑如亞磷酸鹽或膦酸酯加成至亞芳基二氫茚二酮上，經威悌反應合成雜環產物而非過去報導之β-位醯化產物，希望能讓藉由分子內威悌合成雜環產物的方法不再受限於化合物本身的性質。目前已可得到關鍵的中間體加成物，然而使用鹼進行去質子化卻得到難以判斷的化合物或副產物，在未來會持續地進行條件篩選期望合成出目標產物。

Over the past six years, our group has reported on organocatalytic asymmetric cascade reactions used for the synthesis of a complex structure with five quaternary stereocenters. The complex quadruple cascade reaction is triggered by the dynamic kinetic resolution via vinylogous Michael addition of 5-methyl-substituted pyrazolone derivatives to fully substituted enones with trifluoromethyl acetyl group, providing the adduct with complex caged scaffolds with high yields and enantioselectivities successfully. When a 5-phenyl-substituted pyrazolone derivative was used for nucleophilie, the vinylogous Michael addition/tautomerization occur, followed by a key proton transfer step. In the subsequent cascade reaction, a spirocyclic-pyrazolone product with a contiguous 5/5/6-ring is successfully constructed. This reaction holds potential for research in asymmetric diversity-oriented synthesis.Our goal is to synthesize heterocyclic products using different types of phosphine reagents such as alkylphosphites or phosphonates, instead of the reported β-acylation products. We aim to overcome the substrate-dependency issue and generate the Wittig products. Recently, we can successfully get the phosphonate adduct. In future, we will conduct condition screening in order to achieve the synthesis of the desired target product.