鹵化鐵輔佐六員環2－烯炔醯胺與2,3－環氧基炔醯胺合環反應：分別合成具立體選擇性的八氫吲哚酮與雙環㗁唑啶

Abstract

本文分為兩個主題，分別探討路易士酸輔佐六員環2－烯炔醯胺與六員環2,3－環氧基炔醯胺化合物，進行分子內環化反應，合成含氮雙環化合物。 第一章使用六員環2－烯炔醯胺為起始物，在鹵化亞鐵輔佐下，乾燥空氣中進行分子內環化反應，得到含四個立體中心的單一鹵化雙環γ－內醯胺化合物。其立體選擇的關鍵步驟在於利用鐵活化雙鍵並產生立體障礙使鹵素離子與鐵金屬中心行反式加成在雙鍵上。此反應的優點是操作簡單、產率高、得到唯一的立體異構物、好的官能基容忍度與溫和的條件，並不需額外添加氧化劑就可以合成鹵化雙環γ－內醯胺化合物。

第二章使用六員環2,3－環氧基炔醯胺化合物以三鹵化鐵輔佐，於氮氣中室溫下進行分子內環化反應，得到含三個立體中心及雙鍵位相的單一鹵化雙環(口咢)唑啶化合物。此反應的優點是操作簡單、不錯的產率、良好的立體選擇性、反應時間短與條件溫和。Chapter I, a novel synthesis of halogenated bicyclic γ-lactams with four stereogenic centers is developed. Treatment of iron(II) halides with six-membered ring 2-enynamides in THF under dry air afforded halogenated bicyclic [4.3.0] γ-lactams in good yields. The key feature in this reaction involving an anti-addition of a halide ion and the iron center across the activated double bond. The reactions are procedurally simple, high yielding, and excellently diastereoselective, producing bicyclic γ-lactams under mild conditions without additional oxidizing agents.

Chapter II, an efficient synthesis of halogenated bicyclic oxazolidines with four stereogenic centers is reported. Treatment of iron(III) halides with six-membered ring 2,3-epoxy-1-ynamide in ether under nitrogen proceeds rapidly to afford halogenated bicyclic [4.3.0] oxazolidines in moderate yields. The reactions are procedurally simple, efficient and excellently diastereoselective, producing halogenated bicyclic oxazolidines under mild conditions.