稀土化合物催化合成磷膦酸酯和磷杂环戊烷研究.pdf

SOOCHOW UNIVERSITY
硕士学位论文

论文题目稀土化合物催化合成磷(膦)酸酯和
磷杂环戊烷的研究
研究生姓名张艾娇
指导教师姓名徐凡
专业名称有机化学
研究方向有机合成
论文提交日期 2013 年 4 月
稀土化合物催化合成磷(膦)酸酯和磷杂环戊烷的研究中文摘要

中文摘要

本论文主要研究了稀土化合物催化合成α-酰基磷酸酯,γ-氧代膦酸酯以及 2-
氧杂磷杂环戊烷的工作。论文的具体内容包括以下三部分:
1. 考察了硅氨基稀土化合物[(Me3Si)2N]3Ln(-Cl)Li(THF)3 催化的亚磷酸二乙
酯与苯偶酰的反应。该反应通过一个串联的 phospha-aldol-Brook 重排过程,可在
室温下以中等到高的收率得到一系列α-酰基磷酸酯。论文对可能的反应机理进行
了探索。
2. 考察了中性三芳氧基稀土化合物 Ln(OAr)3(THF)2 催化的亚磷酸二乙酯与查
尔酮发生的 1,4-加成反应,在室温下以高收率得到一系列γ-氧代膦酸酯。该反应条
件温和且具有很好的区域选择性。论文对可能的反应机理进行了探索。
3. 考察了硅氨基稀土化合物[(Me3Si)2N]3Ln(-Cl)Li(THF)3 催化的亚磷酸二乙
酯与α,β-不饱和酮的反应,在较温和的条件下选择性地得到一系列 2-氧杂磷杂环
戊烷。论文对可能的反应机理进行了探索。

关键词:芳氧基稀土化合物;硅氨基稀土化合物;苯偶酰;α-酰基磷酸酯;γ-
氧代膦酸酯;2-氧杂磷杂环戊烷;phospha-aldol-Brook 重排;phospha-Michael 加成;
催化;合成

作者:张艾娇
指导教师:徐凡


I
英文摘要稀土化合物催化合成磷(膦)酸酯和磷杂环戊烷的研究

Study on the Synthesis of Phosphates, Phosphonates,
and Phospha-cyclopentanes by Lanthanide-Catalyzed
Reactions

Abstract

The lanthanide-catalyzed reactions for the synthesis of α-acylphosphates,
-oxophosphonates, and 1,2-oxaphospholanes were studied in this thesis:

1. An efficient method for the synthesis of α-acylphosphates by the lanthanide
silylamides [(Me3Si)2N]3Ln(µ-Cl)Li(THF)3 catalyzed reactions of diethyl phosphite
with benzils was developed, which gave the corresponding products in moderate to high
yields under mild conditions. The possible mechanism involving a phospha-aldol-Brook
arrangement was proposed.

2. Lanthanide aryloxides Ln(OAr)3(THF)2 were found to be highly efficient
catalysts for the selective phospha-Michael addition of diethyl phosphite to chalcones.
-Oxophosphonates were obtained as the only products in high yields under mild
conditions. The possible mechanism of the reaction was proposed.

3. Lanthanide silylamides [(Me3Si)2N]3Ln(µ-Cl)Li(THF)3 were found to be
efficient catalysts for the addition of diethyl phosphite to α,β-unsaturated ketones
affording 1,2-oxaphospholanes in moderate to high yie