Title

鈀金屬催化乙酸丙炔酯與有機鋁試劑 之偶合反應研究

Translated Titles

Palladium-Catalyzed Cross-Coupling Reaction of Organoaluminum Reagents with Propargyl Acetates

DOI

10.6845/NCHU.2012.01387

Authors

鄭仲淵

Key Words

鈀金屬催化 ; 丙二烯 ; 有機鋁金屬試劑 ; 偶合反應 ; Palladium-catalyzed ; Cross-coupling ; Organoaluminum Reagent ; Allene

PublicationName

中興大學化學系所學位論文

Volume or Term/Year and Month of Publication

2012年

Academic Degree Category

碩士

Advisor

高漢謀

Content Language

繁體中文

Chinese Abstract

本研究以有機鋁金屬試劑在偶合取代反應的應用為研究目標,論文內容以乙酸丙炔酯與有機鋁試劑在鈀金屬與三芳香基膦配位基的催化下進行偶合反應之研究,並且探討影響偶合反應的因素,其中包含有鈀金屬催化試劑種類、配位基、鋁金屬試劑之劑量、溶劑種類、溫度表現及不同取代基之乙酸丙炔酯的影響。 研究結果顯示,1 mol%醋酸鈀與2 mol%三鄰甲苯基膦在四氫呋喃、室溫下,搭配三甲基鋁與乙酸丙炔酯化合物進行偶合反應,反應只需3小時,其產物產率最高可達94%。 針對不同取代基之乙酸丙炔酯,在1 mol% 醋酸鈀催化下,不僅在芳香環上修飾推電子基(如:甲基及甲氧基)可得到優越的產率,對於拉電子基(如:氯基及三氟甲基)亦可得到極佳的效果。 本催化系統不僅在具芳香族之乙酸丙炔酯上有傑出的催化活性表現,若以反應性較低的非芳香族之乙酸丙炔酯為起始物反應溫度為60 OC的情況下,也具有極高的催化活性;甚至三芳香基鋁金屬試劑進行此偶合反應也可得到具高位向選擇性之丙二烯化合物。

English Abstract

This thesis describes a simple and economic palladium(II) acetate/phosphine catalytic systems which catalyze cross-coupling reactions of organoaluminum reagents with a variety of substituted propargyl acetates for the synthesis of 1,1,3-trisubstituted or 1,3-disubstituted allenes. Effects of ligands, coordinating or non-coordinating solvents, amounts of organoaluminum reagents, ratios of ligand to metal, and reaction times were studied. Cross-couplings of a variety of propargyl acetates catalyzed by 1 mol% palladium(II) acetate and 2 mol% tri(o-tolyl)phosphine were performed on trimethylaluminum in tetrahydrofuran at room temperature only in 3 hours to afford the SN2’ substituted allenes in good to excellent yields of up to 94 %.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系所
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Times Cited
  1. 黃薏陵(2012)。C1對稱氮異環亞甲基和雙牙烷氧基氮異環亞甲基之合成及其化合物和鈀金屬催化有機鋁金屬試劑與炔丙酸乙酯偶合反應之研究。中興大學化學系所學位論文。2012。1-92。