鹵化鐵輔佐3-(5-芳香戊-4-炔基)-2,3環氧基-環己-1-醇與環型2-烯-1炔胺的環化反應

Abstract

本論文主要是利用氯化鐵對分子帶有炔基與其他官能基進行分子內的環化反應，可分為三大主題：炔基環氧基醇類化合物、烯基炔醯胺化合物、炔烯炔醯胺化合物的分子內環化反應。氯化鐵是一種便宜且對環境友善的金屬試劑。 一、 炔基環氧基醇類化合物以六水合三氯化鐵催化，在溫和的反應條件下行分子內環化反應可以得到螺旋雙環化合物，炔基攻打被鐵活化後的環氧基，形成丙烯基碳陽離子，再經由1,5-氫負離子轉移後得到螺[4.5]醇酮化合物。此反應可以控制三個立體中心、有優異的非鏡像選擇性及不錯的產率。 二、 氯化亞鐵輔佐內醯胺化合物的合成：將五員環的2-烯-1-炔醯胺化合物溶於四氫呋喃在氯化亞鐵及水的幫助下得到氧化後的內醯胺化合物，反應條件溫和、且溶劑對環境友善，此反應可同時控制四個立體中心、良好的非鏡像選擇性及不錯的產率。 三、 利用三氯化鐵與環己或環戊2-烯-3-炔-炔醯胺化合物在二氯甲烷、攝氏零度的條件下，經由重排、氯化反應後得到含氯雙環[3.2.1]及[2.2.1]骨架衍生物，反應快速、有良好的產率，且為單一非鏡像選擇性產物。This dissertation contains three topics and focus on iron halides promoted cyclization reactions. Iron halides are easily accessiable, cheap, and evrionmentally friendly reagents. Part I, the FeCl3∙6H2O catalyzed spiroannulation /1,5-hydride transfer of the alkynyl epoxides is described. Hydride transfer from the carbinol carbon to the newly formed cation center furnished α-hydroxyspiro[4.5]decaones in excellent stereoselectivity and good yields. Part II, the iron(II) chloride promoted cyclization reaction of cyclic-2-ynamides has been developed. The reactions were carried out under mild conditions and produced halogenated bicyclic [3.3.0] γ-lactams with four stereocenters with excellent stereoselectivity and in moderate yields. Part III, the iron (III) chloride promoted rearrangement/carbohalogenation of 3-(2-arylethynyl)-cyclohex- and panta-2-en-1-ynamines is described. This process involves a ketenimine rearrangement/carbochlorination affording bicyclo[3.2.1]oct-6-en-6-amines and [2.2.1]hept-2-en-2-amines in good to excellentyields with complete stereoselectivity. The reaction path was suggested confirmed by a double crossed experiment. The futher application of this ketenimine rearrangement is under current investigation.