一價銠金屬催化具鏡像選擇性之分子內1,4-加成反應：合成3-芳基-1-二氫茚酮

Abstract

本篇論文敘述使用一價銠金屬及含有醯胺取代的掌性雙環[2.2.1]雙烯配基L2h所形成之催化劑，以1,4-二噁烷為溶劑，反應溫度為100 ℃，使用1 M碳酸氫鈉水溶液作為添加劑，針對含有α,β-不飽和烯酮之芳基硼酯化合物1進行不對稱分子內1,4-加成反應，生成一系列掌性3-芳基-1-二氫茚酮產物2。總共有27個例子，產率最高達到98%，鏡像超越值最高則是達到99%。另外，利用3號位置具有芳基取代的掌性1-二氫茚酮化合物2g進行非鏡像選擇性酮基還原反應及胺化反應，可以順利合成(+)-Indatraline [(+)-7]藥物，兩步產率分別為77%及54%。This thesis describes an enantioselective intramolecular 1,4-addition reactions of pinacolborate derivatives containing chalcones 1 in 1,4-dioxane at 100 ℃ employing aqueous sodium bicarbonate solution as an additive in presence of 3.0 mol% of Rh(I)-catalyst in situ generated from the [Rh(C2H4)2Cl]2 and the chiral bicyclo[2.2.1]heptadiene ligand bearing a diethyl amide group L2h. This synthetic protocol offers an easy way to obtain a series of chiral 3-aryl-1-indanone derivatives 2 in up to 98% yield and with up to 99% ee.