Asymmetric Construction of Bicyclic [3.1.0] Compounds and Its Application

双环[3.1.0]化合物的不对称结构及其应用

基本信息

批准号：
15590007
负责人：
ABE Hitoshi
金额：
$ 2.3万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

Highly stereoselective syntheses of chiral bicyclic [3.1.0] compounds have been developed by several methods. On a way of this research project, some total syntheses of natural products were also achieved by a palladium-mediated biaryl coupling reaction of phenyl benzoate derivatives.1.A Reaction of σ-Symmetric Ketone CompoundsA symmetric ketone was prepared as the substrate, through the Meinwald rearrangement of norbornadiene. An enentioselective deprotonation reaction was attempted using several chiral amide bases. This reaction was quite successful to produce an optically active bicycle[3.1.0] compound with high enantioselectivity.Next, a symmetric epoxyketone was examined on the enantioselective deprotonation reaction using chiral amide bases. This reaction was also successful to generate the corresponding enolate followed by a transannular carbon-carbon bond formation accompanying an epoxy opening. The obtained product was transformed into the optically active bicyclo[3.1.0] compound with high optical purity.2.Optical Kinetic Resolution Using the Baker's YeastAn optical kinetic resolution of a racemic bicyclo[3.1.0] compound using the baker's yeast was attempted. After various examination of the reaction conditions and work-up methods, we found that this technique was effective to give the optical active bicycle[3.1.0] compound with high stereoselectivity. The optical purity and the absolute configuration were determined by comparison with a reported information.

多种方法开发了手性双乳剂[3.1.0]化合物的高度立体选择性合成。在该研究项目的一种方式中，还通过钯介导的苯基苯基苯甲酸酯衍生物的二型偶联反应来实现天然产物的一些总合成。1。σ对称酮复合酮对称酮的反应是通过Meinwald Rebrangement的Norrangement of Nybornaradiene的Meinwald Recrate制备的。使用多个手性酰胺基碱基尝试使用肾上腺素化反应。这种反应非常成功地产生了使用手性酰胺碱基的高对映选择性去质子化反应的光学活性自行车[3.1.0]化合物。该反应也成功地产生相应的烯烃，然后产生跨碳碳键的形成涉及环氧树脂开口。将获得的产物转化为具有高光纯度的光学活性双环状[3.1.0]化合物。2。使用面包质bicycleclo [3.1.0]化合物的贝克酵母光学分辨率的光学动力学分辨率尝试使用面包师的酵母。经过各种反应条件和解决方法的检查后，我们发现该技术有效地给具有高立体选择性的光学活性自行车[3.1.0]化合物。通过与报告的信息进行比较来确定光学纯度和绝对配置。

项目成果

期刊论文数量（16）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Enantioselective Construction of Biaryl Part in the Synthesis of Stegane Related Compounds

苯乙烯相关化合物合成中联芳基部分的对映选择性构建

DOI：
发表时间：
2004
期刊：
Tetrahedron Letters 45(11)
影响因子：
0
作者：
Hitoshi Abe;Hitoshi Abe;Takeshi Kinoshita;Hitoshi Abe;Hitoshi Abe
通讯作者：
Hitoshi Abe

Hitoshi Abe: "Enantioselective construction of biaryl part in the synthesis of stegane related compounds"Tetrahedron Letters. Vol.45, No.11. 2327-2329 (2004)

阿部仁：“丁烷相关化合物合成中联芳基部分的对映选择性构建”四面体快报。

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

An Attempt of Biaryl Coupling Reaction of Benzyl Benzoate Derivatives under Ullman Conditions

乌尔曼条件下苯甲酸苄酯衍生物联芳基偶联反应的尝试

DOI：
发表时间：
2003
期刊：
Heterocycles 61・1
影响因子：
0
作者：
Hitoshi Abe;Hitoshi Abe;Takeshi Kinoshita;Hitoshi Abe;Hitoshi Abe;Takeshi Kinoshita;Takeshi Kinoshita;Hitoshi Abe
通讯作者：
Hitoshi Abe

Enatioselective Construction of Biaryl Part in the Synthesis of Stegane Related Compounds

甾烷相关化合物合成中联芳基部分的对映选择性构建