三溴化鐵輔佐N-炔丙基-N-1-炔醯胺及2-炔-1-炔醯胺化合物的分子內環化反應：溴化-環丁烯胺及-δ-內醯胺衍生物的合成

Abstract

本文分為二個主題，依序探討以鹵化鐵輔佐N-炔丙基-N-1-炔醯胺及2-炔-1-炔醯胺化合物的分子內環化反應，合成含鹵素的環丁烯胺及δ-內醯胺的衍生物。 (一)三溴化鐵輔佐N-炔丙基-N-1-炔醯胺化合物的分子內環化反應，此反應經由N-to-C propargyl shift，再經由aza-Prins-type cyclization得到環丁烯胺化合物。此合環反應時間短、起始物製備容易且使用便宜的三溴化鐵及可得到環丁烯胺化合物。

(二)使用2-炔-1-炔醯胺化合物為起始物，在三溴化鐵的輔佐下，乾燥空氣中進行分子內環化反應，得到δ-內醯胺的衍生物。此反應的優點為起始物製備容易、條件溫和、且並不需要額外添加氧化劑即可得到δ-內醯胺的衍生物。Iron halide-assisted intramolecular cyclization reactions of N-propargyl-N-1-ynylamides and 2-yn-1-ynamides are described. (1) A facile and efficient N-to-C propargyl shift and aza-Prins cyclization sequence of N-propargyl-N-1-ynylamides was promoted by iron(III) bromide, generating cyclobutenamines. This reaction involves an unprecedented formation of a ketenimine via Fe(III)-assisted N-to-C propargyl rearrangement, followed by aza-Prins cyclization. Using the inexpensive iron(III) bromide to construct cyclobutenamines in short reaction time is advantage of the reaction.

(2) Treatment of iron(III) bromide with 2-yn-1-ynamides in THF under dry air afforded halogenated δ-lactams. Using readily available starting materials and inexpensive iron(III) bromide to construct δ-lactams under mild conditions without additional oxidizing agents in short reaction time are advantages of the reaction.