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Development of a Highly Stereoselective Remote Asymmetric Induction Method by Means of the Binaphthalene-Template Conformation Control

通过联萘模板构象控制开发高立体选择性远程不对称诱导方法

基本信息

批准号：
08405058
负责人：
MIYANO Sotaro
金额：
$ 23.1万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1998
项目状态：
已结题

项目摘要

We have developed diastereoselective asymmetric reactions using the 2,2'-positions of 1, l'-binaphthyl compounds as a chiral field. Synthesis of novel binaphthyls and thiacalixarenes and exploration of the functions of the latter compounds are the other targets of this research. The summary of the results is itemized as follows : 1. Treatment of gamma-keto esters of l , 1'-binaphthyl-2-ol bearing an appropriate oligoether tether at the 2'-position with DIBAL-H in the presence of magnesium bromide gave, after LAH reduction of the resulting diastereomeric hydroxy esters, I , 4-diols with high enantiomeric excesses. On the other hand, Grignard reaction of the relevant gamma-keto esters gave gamma-lactones having a chiral quaternary carbon center with up to 99% ee. 2. The remote asymmetric inductive Grignard reaction was found to be applicable to delta- and epsilon-keto esters and was advantageously utilized for the synthesis of a marine antibiotic, malyngolide. 3. The corresponding Grignard reaction of zeta- to theta-keto esters was realized by using BINOL as the chiral auxiliary. Thus, the Grignard reaction of the mono omega-keto esters of BINOL in the presence of magnesium bromide proceeded with more than 80% de. 4. Several binaphthyl compounds were effectively prepared in an atropisomeric or racemic form via the nucleophilic aromatic substitution on 1-alkoxynaphthalenes bearing an ester, sulfonyl, or nitro group at the 2-position as the activating group by 1-naphthyl Grignard reagents. 5. A novel calixarene, p-tert-butylthiacalix[4]arene, which is expected to be a potential substitute for BINOL framework, was effectively prepared from p-tert-butylphenol and powdered sulfur. The derivatives were found to function as a host molecule to bind specific metal ions and toxic halogenated organic compounds and as a chirality-recognizing element for a stationary phase for gas chromatography.

我们使用 1,1'-联萘化合物的 2,2'-位作为手性场开发了非对映选择性不对称反应。新型联萘和硫杂杯芳烃的合成以及后一化合物的功能探索是本研究的其他目标。结果概述如下： 1.在溴化镁存在下，用DIBAL-H处理2'-位上带有合适的低聚醚系链的1，1'-联萘-2-醇的γ-酮酯，在所得非对映体羟基酯的LAH还原后，得到具有高对映体过量的1，4-二醇。另一方面，相关γ-酮酯的格氏反应得到具有手性季碳中心且ee高达99%的γ-内酯。 2.发现远程不对称诱导格氏反应适用于δ-和ε-酮酯，并有利地用于合成海洋抗生素马林高内酯。 3.以BINOL为手性助剂，实现了zeta-酮酯相应的Grignard反应。因此，BINOL 的单 omega-酮酯在溴化镁存在下进行的格氏反应超过 80% de。 4.通过1-萘基格氏试剂对2位带有酯基、磺酰基或硝基作为活化基团的1-烷氧基萘进行亲核芳香取代，有效地制备了几种阻转异构体或外消旋形式的联萘化合物。 5. 以对叔丁基苯酚和粉状硫为原料，有效制备了一种新型杯芳烃，即对叔丁基硫杂杯芳烃[4]芳烃，有望成为BINOL骨架的潜在替代品。研究发现这些衍生物可作为主体分子结合特定金属离子和有毒卤代有机化合物，并作为气相色谱固定相的手性识别元素。