路易士酸輔佐分子內聯繼反應: 合成吡咯、呋喃及螺旋化合物

Abstract

本文共有二個主題，首先是利用1.2當量三氟甲磺酸三甲基矽酯(TMSOTf)輔佐2-(4-芳香基炔丙胺基甲基)-3,5,5-三甲基-2,3-環氧基環己-1-酮經聯繼反應合成吡咯化合物。反應會經由串列semi-pinacol重排反應/炔基–酮基置換反應得到。使用1.0當量三氟化硼(BF3•OEt2)輔佐2-(4-芳香基炔丙氧基甲基)-3,5,5-三甲基-2,3-環氧基環己-1-酮經由相同反應機構合成呋喃化合物。 最後是合成螺旋化合物經由三溴化鐵(FeBr3)輔佐3-(4-芳香基-炔丙胺基-甲基)-2,3-環氧基環己-1-酮經聯繼反應得到。反應會經由串列semi-pinacol重排反應/炔基–醛基置換反應得到。

This thesis contains two topics. The first part is the synthesis of pyrroles via 1.2 equiv TMSOTf-promoted tandem reaction of 2-(4-arylpropargylamino- methyl)-3,5,5-trimethyl-2,3-epoxy-cyclohexa-1-ones. The reaction underwent a tandem semi-pinacol rearrangement/alkyne-ketone metathesis to obtain pyrroles. While 1.0 equiv BF3•OEt2 is required for the synthesis of the furans from 2-(4-aryl-propargyloxymethyl)-3,5,5-trimethyl-2,3-epoxy-cyclohexa-1- ones. The second part is the synthesis of azaspirocycles via FeBr3-promoted tandem reaction of 3-(4-arylpropargylaminomethyl)-2,3-epoxy-cyclohexa-1- ones. The reaction underwent a tandem semi-pinacol rearrangement/alkyne– aldehyde metathesis.