一、透過鹼控制高醯基香豆素與 1,3-茚二酮衍生物進行化學選擇 性 1,6-Addition/Aldol 或 1,6-Addition/Michael 連續反應合成 香豆素衍生物 二、透過有機膦試劑、酸酐與亞芳基-1,3-茚二酮合成茚並 [1,2-c]呋喃衍生物

Abstract

第一部分為利用本實驗室開發之高醯基香豆素以及 1,3-茚二酮衍生物進 行連續性反應，並藉由改變其反應條件，希望能控制其反應之化學選擇性來達到多樣性導向合成反應，並建構具有生物活性應用之產物。 此研究利用高醯基香豆素衍生物與β-酯基芳基亞烯基-1,3-茚二酮衍生物 進行 1,6-加成反應後，因其中間體 dienolate 具有高度活性，可利用控制反應條件來進行 Aldol 或 Michael 之選擇性加成，達到連續性之多樣性導向合成反應，且得到兩種香豆素類似物之骨架。 第二部分為實驗室先前研究之延伸，利用1,3-茚二酮烯類化合物衍生物與有機膦試劑進行反應，經過重排反應後可得一具有三環結構之呋喃化合物，本研究為優化其反應條件並針對其反應機制進行相關探討。Part I : Herein, we demonstrated two vinylogous cascade reactions where in the chemoselectivity is controlled effectively by using two distinct bases resulting in diverse coumarin derivatives. These coumarin derivatives were synthesized through two different cascade reactions viz 1,6-Addition/Aldol addition and 1,6Addition/Michael addition from 3-homoacylcoumarins2 and 2-cinnamylidene-1,3indandiones. By careful optimization of reaction conditions, the selective synthesis of two kinds of coumarin derivatives was achieved successfully in good yields and good diastereoselectivities. Part II : In 2014 we have developed a organophosphane-mediated reaction to do the βacylation and wittig reaction. Although we got β-acylation product, we didn’t get the wittig reaction product. Instead we’ve got a rearrangement product 8H-indeno[1,2c]furan-8-one. In this research we optimized the standard protocol for the synthesis and study the mechanism for the rearrangement reaction