一價銠金屬/掌性雙環 [2.2.1] 雙烯配體催化環酮亞胺的不對稱烯丙基化反應

Abstract

本論文探討以一價銠金屬與掌性雙環 [2.2.1] 雙烯配體 L12j 所形成之錯合物為催化劑，以1,4-二噁烷為溶劑在加熱至60 °C的反應條件下，進行烯丙基三氟硼酸鉀鹽試劑 31 對環酮亞胺 30 的不對稱1,2-加成反應，以合成出一系列具高鏡像選擇性的掌性四級碳高烯丙基胺類化合物 43、65和66，產率最高可達99%，鏡像選擇性最高可達99%，非鏡像異構物比值最高可達5.5:1.0。

In this thesis, we focused on development new methodology to synthesize various enantioenriched α-tertiary homoallylic amines by Rhodium(I) catalyst which prepared in situ from Rh(I) catalyst precursor and chiral bicyclic [2.2.1] diene ligand L12j. Rhodium(I) complex catalyzed enantioselective 1,2-addition reactions of potassium allyltrifluo-roborates 31 with cyclic ketimines 30 was found to be highly efficient to afford the desired products with up to 99% yield, 99% ee and 5.5:1.0 dr.