Asymmetric reactions controled with moleculary imprinted polymers.

用分子印迹聚合物控制的不对称反应。

• 批准号: 15590013
• 负责人: ISHIZUKA Tadao
• 金额: $ 2.24万
• 依托单位: Kumamoto 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15590013/
• 关键词: Moleculary Imprinting; Asymmetric synthesis; Polymer; Diamine; Amino alcohol; 不斉合成; 不斉触媒

Molecularly imprinted polymers were synthesized by use of bicyclic chiral aminoalcohols as template. The difference of affinities between the template molecule and other aminoalcohols to the polymers were detected by HPLC analysis, selective adsorbtion of templete molecule were observed. Moreover, the templete aminoalcohols showed priority in adosorbtion to the imprinted polymer over its enantiomer.Asymmetric reactions with template molecules as catalysts were examined. Sulfonamides, thiazolines and thioethers with bicyclic skeleton were successfully utilized in hydrogen-transfer reduction of ketones, the Diels-Alder reactions and π-allyl alkylations, respectively. These compounds showed not only high yields and excellent selectiveties but marvelous character that cannot be affected by sterically bulkyness of substrate.These catalysts might be good templetes of imprinted polymers because of these basic characters and restricted conformations. Further investigations will be needed for application of the imprinted polymers to these asymmetric reactions.

以双环手性氨基醇为模板合成了分子印迹聚合物。用HPLC分析了模板分子与其他氨基醇对聚合物亲和力的差异，发现模板分子对聚合物有选择性吸附。此外，模板氨基醇对印迹聚合物的吸附优先于对映体。具有双环骨架的磺酰胺、噻唑啉和硫醚分别成功地用于酮的氢转移还原、Diels-Alder反应和π-烯丙基烷基化反应。这些化合物不仅具有较高的产率和选择性，而且具有不受底物体积影响的优良性质，这些基本性质和构象的限制使其有望成为印迹聚合物的理想模板。将印迹聚合物应用到这些不对称反应中还需要进一步的研究。

项目成果

Sterically congested "roofed" 2-iminothioethers as new chiral ligands for palladium-catalyzed asymmetric allylic alkylation

• DOI: 10.3987/com-05-s(k)50
• 发表时间: 2005-12
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: Ryoh Tokuda;H. Matsunaga;T. Ishizuka;M. Nakajima;T. Kunieda

Chiral phosphine oxide BINAPO as a catalyst for enantioselective allylation of aldehydes with allyltrichlorosilanes

• DOI: 10.1016/j.tetlet.2004.10.168
• 发表时间: 2005-01-03
• 期刊: TETRAHEDRON LETTERS
• 影响因子: 1.8
• 作者: Nakajima, M;Kotani, S;Hashimoto, S
• 通讯作者: Hashimoto, S

Catalytic dissymmetrization of meso-2-imidazolidinones : alternative route to chiral synthons for 1,2-diamines

内消旋-2-咪唑啉酮的催化不对称化：1,2-二胺手性合成子的替代途径

• 发表时间: 2004
• 期刊: Tetrahedron Letters 45
• 作者: Ishizuka;T.;Makoto Nakajima;Tadao Ishizuka
• 通讯作者: Tadao Ishizuka

Sterically Congested "Roofed" 2-Thiazolines as New Chiral Ligands for Copper(II)-Catalyzed Asymmetric Diels-Alder Reactions

空间拥挤的“屋顶”2-噻唑啉作为铜(II)催化不对称狄尔斯-阿尔德反应的新手性配体

• 发表时间: 2005
• 期刊: Tetrahedron Letters 46
• 作者: Yamakuchi;M.
• 通讯作者: M.

Enantioselective aldol reaction of trimethoxysilyl enol ether catalyzed by lithium binaphtholate

• DOI: 10.1021/ol048485
• 发表时间: 2004-10-14
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Nakajima, M;Orito, Y;Hashimoto, S
• 通讯作者: Hashimoto, S