Construction of chiral reaction environment based on spontaneous resolution of organic compounds

基于有机化合物自发拆分的手性反应环境构建

• 批准号: 16590011
• 负责人: AZUMAYA Isao
• 金额: $ 1.47万
• 依托单位: Tokushima Bunri University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16590011/
• 关键词: Chiral transformation; Sulfonamide; Spontaneous resolution; X-ray crystallographic analysis; Crystal structure; Stereochemistry

1)A chiral crystal of benzenesulfonanilide was used as an asymmetric ligand in addition reaction of ethyl group to Chalcone under the condition of diethylzinc and copper triflate. Any enantio excess of products, however, was not observed.2)Other sulfonamides which show spontaneous resolution were explored. Substituted benzenesulfonyl chloride and substituted aniline with ether group etc. at the o-position of the benzene ring for metal coordination or to be slower in racemization were synthesized. In the result, it was found that 5 of 40 sulfoanilides showed spontaneous resolution.3)The protocol in which compounds that show spontaneous resolution are searched effectively in shorter time was modified in combination with parallel synthesis using polymer-supported base, evaporation of filtrate to dryness with stirring, and solid state CD spectrum measurement. According to the procedure, it was found that 4 sulfonamides out of 12 combinations of sulfonyl chlorides and anilines, judging by the Cotton effect.4)Crystallization was carried out under an irradiation of circular polarized light, but chiral induction was not observed in an enantiomer ratio of the sulfonamides which showed spontaneous resolution.5)On the course of the investigation into the spontaneous resolution of aromatic sulfonamides, all the aromatic sulfonamides were found to exist in synclinal form in the crystal, some of which formed in intermolecular double hydrogen bonds.

1）在二乙基辛和三磷酸铜的条件下乙基甲基的手性晶体被用作不对称配体。但是，没有观察到任何对照过量的产品。2）探索了自发分辨率的其他磺酰胺。合成了取代的苯磺酰氯氯化物，并用苯基组取代苯胺等。在苯环的O位置上以金属协调或在种族化中的速度较慢。结果，发现在40个硫酸硫代中的5个中有5个显示出自发的分辨率。3）在较短的时间内有效地搜索了表明自发分辨率的化合物，并使用平行的合成使用聚合物支持的碱基，将液体蒸发与液态和固态CD CD exprement和固体测量相结合。根据该程序，发现从棉花效应的12种组合中，有4种磺酰胺在棉花效应中进行判断。4）在圆形极化光的辐照下进行结晶，但在对硫代剂的映射中没有观察到的硫氧化苯甲酸的概念。磺酰胺，所有芳族磺酰胺均在晶体中以突出形式存在，其中一些形成在分子间双氢键中。