文档介绍：新型手性二茂铁配体的合成和应用研究
摘要
不对称催化是获得手性化合物的最有效和最有利的方法之一,是当前有机化学
研究的一个热点。配体的设计和合成是不对称催化的关键问题,二茂铁及其特殊结
构的发现,在手性配体的设计和合成中具有非常重要的意义。本论文合成了一系列
新型手性二茂铁配体,并对其催化性质进行了研究,所做工作主要包括两个方面:
以二茂铁和 L-丝氨酸甲酯盐酸盐为起始原料合成了新型 C2 对称的手性二茂铁 N, N,
O, O 类配体 1,并将此配体成功应用于二乙基锌对醛的不对称加成反应中,得到了
最高达 94%的 ee 值。合成了相应的 C1 对称的手性二茂铁 N, O 配体 2,通过比较此
配体与 C2 对称的手性二茂铁 N, N, O, O 配体在二乙基锌对醛的不对称加成反应中的
催化效果,提出了一个具有双金属核的催化机理。同时,通过手性二茂铁双噁唑啉
的选择性邻位锂化合成了 C2 对称的 1,1’,2,2’四取代手性二茂铁双噁唑啉配体 3,并
在 3 的基础上通过修饰进一步合成了 C2 对称的只具有面手性的二茂铁双瞵配体 4。
配体 3 和配体 4 在金属钯催化的烯丙基取代反应中已经显示了很好的催化活性和催
化效果,进一步的不对称催化应用正在进行中。

关键词:二茂铁,不对称催化,N, N, O, O 配体, 双噁唑啉配体,双膦配
体
I ––
SYNTHESIS AND APPLICATION OF NOVEL CHIRAL
FERROCENE LIGANDS

ABSTRACT

Asymmetric catalysis is one of effective ways to obtain chiral
compounds. The design and synthesis of chiral ligands is the key to develop
the asymmetric catalysis. Since the discovery of ferrocene in 1951, chiral
ligands with a ferrocene backbone have received much attention in the past
decades because of their special structure. This thesis reported the synthesis
of novel ferrocene ligands and their applications in the asymmetric reactions.
The major work included two parts. The first part is the research on the
synthesis and application of novel chiral C2-symmetric N, N, O, O ligand 1
with a ferrocene backbone and a hydroxyl group at the substituent of the
oxazoline ring. This kind of ligands can be easily prepared from
1,1’-ferrocenedicarboxylic acid dichloride and L-serine methyl ester
hydrochloride with three steps in high overall yields. Their applications in
the asymmetric alkylation of arylaldehyde with diethylzinc were studied and
up to 94% ee was obtained with these ligands. A possible binuclear zinc
catalytic mechanism was also proposed paring the catalytic effect of
the corresponding C1-symmetric ligand 2 with the C2-symmetric ones. The
second part is the development of C2-symmetric 1,1’,2,2’-tetrasubstituted
chiral bisoxazoline ferrocen