Preparation of Nitrogen Containing Optically Active Compounds
Abstract
中文摘要
本論文旨在敘訴利用不同的合成方法合成出的掌性含氮化合物。論文共分為四個章節，分述如下：
第一章 概論
本章說明掌性含氮化合物的重要性。分別簡單說明胺基酸，胜肽，以及藥物的掌性分子之活性與掌性含氮化合物為掌性配體在不對稱反應上的應用。
第二章 由三取代丙烯醇合成高非鏡像選擇性之丙烯胺化合物並利用來製備掌性α-取代的丙氨酸乙酯
在這個部分中我們探討的是以三甲基鋁在鋯的催化下與炔類化合物反應製備出的乙烯基鋁試劑與醛類進行加成反應，得到具高立體選擇性之三取代丙烯醇化合物。這些三取代丙烯醇化合物接著進行 Overman 反應，建立了掌性的烯丙基胺化合物，此方法可以利用來合成掌性α-取代的丙氨酸乙酯。
第三章 銠金屬催化三氟硼酸鉀對芳香亞胺進行不對稱烯基化反應
本章節敘訴以掌性雙烯配體與銠金屬形成之催化劑催化三氟硼酸鉀化合物與芳香亞胺化合物之進行不對稱加成反應。此催化反應提供了一個有效合成具有高鏡像超越值的掌性烯丙胺類化合物 。
第四章 微波輔助銠金屬催化三氟硼酸鉀對亞胺進行烯基化催化不對稱反應
在這部分，我們探討將上一章節利用加熱進行不對稱加成反應以微波促進的方式進行。經由微波促進，掌性雙烯配體與銠金屬形成之催化劑催化三氟硼酸鉀化合物與芳香亞胺化合物之進行不對稱加成反應，反應可以在幾個小時內結束而且只需要1 mol%的銠催化劑也得到很好的鏡像超越值。
Abstract The research work presented in this dissertation is highlighted the importance of nitrogen containing chiral compounds its synthesis through various methods. Thesis is divided into four chapters as mentioned below. Chapter 1. General Introduction This chapter deals with the importance of nitrogen containing chiral compounds in nature and in human life. Importance of amino acids, peptides, chiral drug molecules in pharmaceuticals and as a chiral ligands used for asymmetric reactions. Chapter 2. Preparation of Chiral -Substituted Alaninates Through an Efficient Diastereoselective Synthesis of Tri-substituted Allylic Alcohols. In this part we have discussed the addition of vinylaluminium reagents, produced by the zirconium catalyzed carboalumination of various alkynes and Me3Al, to the easily accessible aldehyde (3) afforded the corresponding trisubstituted allylic alcohols with excellent diastereoselectivities. A subsequent Overman reaction led to an efficient and highly stereoselective construction of allylic amines containing chiral quaternary carbon stereocentres. The utility of this method was demonstrated for the synthesis of chiral -Substituted Alaninates. Chapter 3. Highly Enantioselective Rh-Catalyzed Alkenylation of Imines: Synthesis of Chiral Allylic Amines via Asymmetric Addition of Potassium Alkenyltrifluoroborates to N-Tosyl Imines. Simple N-tosyl aryl aldimines, prepared from the condensation of para tolyl sulfonylamide and aromatic aldehydes, can be used as substrates in the rhodium catalyzed 1,2- addition reaction using alkenyl boron nucleophiles. In the presence of 1.5 mol % of [RhCl(29f)]2, enantioselective addition of various potassium alkenyltrifluoroborates to various aryl aldimines furnished the corresponding chiral allylic amines in good yields and good to excellent ee. Chapter 4. Microwave-Assisted Enantioselective Addition of Potassium alkenyl trifluoroborates to aldimines catalyzed by Rh/diene catalyst. In this part we have reportedour recent studies on microwave assisted asymmetric reaction. Use of simple N-protected simple aryl aldimines and its addition with alkenyl potassium trifluoroborates. Preparation of chiral allylic amines was achieved in presence of chiral catalyst which was in situ generated using 0.5 mol % of [RhCl(C2H4)2]2 and Ligand 29e (1.2 mol %) with moderate to high yield (40-96%), and 86-98% ee.
Abstract The research work presented in this dissertation is highlighted the importance of nitrogen containing chiral compounds its synthesis through various methods. Thesis is divided into four chapters as mentioned below. Chapter 1. General Introduction This chapter deals with the importance of nitrogen containing chiral compounds in nature and in human life. Importance of amino acids, peptides, chiral drug molecules in pharmaceuticals and as a chiral ligands used for asymmetric reactions. Chapter 2. Preparation of Chiral -Substituted Alaninates Through an Efficient Diastereoselective Synthesis of Tri-substituted Allylic Alcohols. In this part we have discussed the addition of vinylaluminium reagents, produced by the zirconium catalyzed carboalumination of various alkynes and Me3Al, to the easily accessible aldehyde (3) afforded the corresponding trisubstituted allylic alcohols with excellent diastereoselectivities. A subsequent Overman reaction led to an efficient and highly stereoselective construction of allylic amines containing chiral quaternary carbon stereocentres. The utility of this method was demonstrated for the synthesis of chiral -Substituted Alaninates. Chapter 3. Highly Enantioselective Rh-Catalyzed Alkenylation of Imines: Synthesis of Chiral Allylic Amines via Asymmetric Addition of Potassium Alkenyltrifluoroborates to N-Tosyl Imines. Simple N-tosyl aryl aldimines, prepared from the condensation of para tolyl sulfonylamide and aromatic aldehydes, can be used as substrates in the rhodium catalyzed 1,2- addition reaction using alkenyl boron nucleophiles. In the presence of 1.5 mol % of [RhCl(29f)]2, enantioselective addition of various potassium alkenyltrifluoroborates to various aryl aldimines furnished the corresponding chiral allylic amines in good yields and good to excellent ee. Chapter 4. Microwave-Assisted Enantioselective Addition of Potassium alkenyl trifluoroborates to aldimines catalyzed by Rh/diene catalyst. In this part we have reportedour recent studies on microwave assisted asymmetric reaction. Use of simple N-protected simple aryl aldimines and its addition with alkenyl potassium trifluoroborates. Preparation of chiral allylic amines was achieved in presence of chiral catalyst which was in situ generated using 0.5 mol % of [RhCl(C2H4)2]2 and Ligand 29e (1.2 mol %) with moderate to high yield (40-96%), and 86-98% ee.
Description
Keywords
銠金屬, 含氮化合物, 烯丙基胺, 烯丙基醇, Rhodium, Nitrogen compounds, allylic amines, allylic Alcohols