文档介绍：青岛科技大学
硕士学位论文
新型樟脑手性配体的合成及其诱导不对称还原反应的研究
姓名:尤佳
申请学位级别:硕士
专业:药物化学
指导教师:夏亚穆
20100608
青岛科技大学研究生学位论文
新型樟脑手性配体的合成及其诱导不对称还原反应的研究
摘要
天然樟脑,来源丰富价格低廉且易于重结晶,是具有光学活性的天然产物,
具有双环刚性结构,其 C-2 位容易形成立体中心,再进一步反应即可获得多种
衍生物,以它为手性源的不对称合成反应一直是热门的研究课题。本论文研究
了樟脑磺酰胺醇类手性配体对前手性酮的不对称还原反应的诱导活性,并以其
为手性配体对具有生理活性的天然苯并二氢呋喃木脂素类化合物进行不对称合
成,内容共包括以下三部分:
第一部分综述,介绍了樟脑及其衍生物的用途及其在不对称合成中应用的
研究现状,主要对近年来诱导不对称合成的研究做了重点阐述,并结合当前研
究现状提出了本课题研究内容。
第二部分以樟脑为原料合成出一类樟脑磺酰胺醇手性配体,对其诱导不对
称还原反应进行了研究,并在每步反应中考察不同条件,包括温度、溶剂和投
料比对反应的影响,同时对合成路线中的其它方法的试验探索做了详细介绍和
结果分析。
第三部分选择樟脑磺酰胺醇类化合物为手性配体合成了苯并二氢呋喃新木
脂素。对目标化合物合成过程中重要步骤的反应历程、反应中存在的问题、反
应注意事项等进行了阐述和分析。
关键词:樟脑磺酰胺醇不对称还原苯并二氢呋喃新木脂素氧化偶合
I
新型樟脑手性配体的合成及其诱导不对称还原反应的研究
STUDIES ON SYNTHESIS OF CAMPHOR-DERIVED
CHIRAL AUXILIARIES AND ASYMMETRIC REDUCTION
OF CHIRAL a-KETO ESTERS
ABSTRACT
The abundance, crystallinity and manifold transformations of (+)-camphor has
attracted considerable interest throughout the history anic chemistry. By the
rearrangement and functionalizations at C-2, camphor and its derivates has served as
a fascinatingly versatile starting material for the synthesis of enantioerically pure
natural products. This thesis mainly focused on asymmetric reduction of chiral
a-keto esters using camphorsulfonamide alcohol auxiliaries and regioselective
oxidative cross-coupling of dihydrobenzofuran neolignan, including the following
three parts:
Part one, review. The application in asymmetric synthesis and development of
camphor and its derivates within recent ten years were reviewed in this part. After
that the theme of this paper was proposed.
In the second part, natural camphor was used as the starting materials to obtain
a class of camphorsulfonamide alcohol auxiliaries, and the ligands were used in
asymmetric reduction. Each step of the experiment was optimized, including
temperature, solvent and proportion of adding amount. In addition, some other test
methods using in the synthesis of pounds were introduced and analyzed.