XJIPC OpenIR  > 资源化学研究室
Thesis Advisor卢崇道
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Name硕士
Degree Discipline有机化学
Keyword氨基化 烷基酮酯 催化反应 氯化镁、酰基亚硝基化合物

亚硝基化合物是一类具有高活性的反应中间体。酰基亚硝基化合物由于其较低的活化能和较小的HOMO-LUMO轨道能级差,与其他亚硝基化合物相比具有更高 的反应活性。研究表明,酰基亚硝基化合物极易发生二聚而无法分离,因此,酰基亚硝基化合物作为氨基化试剂通常需要原位氧化制备。   α-氨基-β-酮酯是β-羟基-α氨基酸的重要前体,同时也是合成其他具有生物活性的含氮杂环的重要组成部分。其中一种构建这种结构的方法是β-酮酯 的α位的直接氨基化。   本论文主要以TBHP作为羟胺氧化试剂、氯化镁作为β酮酯的烯醇化试剂合成α-氨基-β-酮酯。该反应以乙腈作溶剂,40℃条件下最高得到了99%的 产率。研究表明,该反应对脂肪族以及芳香族β酮酯均具有良好的适用性,苯环上连有吸电子基团时有利于该反应的进行。 本论文同时研究了该反应不对称催化反应的可行性。反应以碘化镁作为β酮酯的烯醇化试剂,以(R,R)-2,6-双(4-异丙基-2-恶唑啉-2-基)吡啶 作为手性催化剂,TBHP或MnO2作为羟胺的氧化试剂,初步尝试未得到ee值。

Other Abstract

Nitroso compounds is a highly reactive intermediate. Due to their lower activation energy, acetylnitroso compounds have a higher reactive compared with other nitroso compounds. Acetylnitroso compound is easy to form a dimer and can’t be siolated. As an amination reagent, it always formed in situ by oxidation.   α-Amino-β-ketoesters are potential precursors of β-hydroxy-α-amino acids and of nitrogen-containing heterocyclic compounds that serve as important building blocks in many bioactive agents. One pathway effective for constructing this useful scaffold is direct electrophilic α-amination of β-ketoesters, and various aminating agents have been explored in this procedure.   Here we describe a practical method in which compatible conditions can be ensured, using magnesium chloride to catalyze enolization and tert-butyl hydroperoxide (TBHP) for oxidation. The reaction was performed at 40℃and CH3CN was used as solvent. The reaction has a best yield up to 99%. The scope of the reaction was investigate and good compatibility of aliphatic and aromatic β-ketoester have been observed. What’s more, The benzene ring connected with the electron withdrawing group is in favor of the reaction.   We then tried to extend this catalytic process to asymmetric catalysis, but our efforts proved fruitless. When we used MgI2 as catalyst together with a chiral pybox ligand in the reaction, we obtained α-amination product as a racemic mixture. In addition to TBHP, we tested the mild oxidant MnO2, which gave α-amination product in moderate yield without asymmetric induction.

Document Type学位论文
Recommended Citation
GB/T 7714
梁明强. 氯化镁催化酰基羟胺的氧化N-aldol反应研究[D]. 北京. 中国科学院大学,2014.
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氯化镁催化酰基羟胺的氧化N-aldol反(7849KB)学位论文 开放获取CC BY-NC-SAApplication Full Text
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