Development and Application of Multifunctional Catalysts by Dynamic Stereochemical Control

动态立体化学控制多功能催化剂的开发及应用

• 批准号: 10208209
• 负责人: SASAI Hiroaki
• 金额: $ 13.76万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10208209/
• 关键词: Absolute Asymmetric Synthesis; Chiral Catalyst; Oxidative Coupling; Binaphthol; Chirality Control; Cu; Magnetic field; 遠隔位不斉制御; 触媒; 希土類; ガドリニウム; ビフェノール

Since the origin of chirality in nature and absolute asymmetric synthesis are intimately related, this subject attracts much interest to a number of scientists. Although magnetic field itself is believed to be an achiral physical force, combination use of magnetic field with other physical force has a possibility to generate chirality without any optically active compound. When oxidative coupling reaction of 2-naphthol derivatives was carried out under 1.5〜8T magnetic field in the presence of Cu-catalyst, 1,1'-bi-2-naphthol derivative with small but distinct optical activity was obtained. The enantiomeric excesses were determined by chiral column on HPLC and/or optical rotations of the products. Further studies toward the control of chirality under the magnetic field are in progress.A cross coupling reaction of 6-bromo-2-naphthol with 2-naphthol was also examined. The desired 6-bromo-1,1'-bi-2-naphthol was obtained predominantly in the presence of radical inhibitor.

由于自然界中手性的起源与绝对不对称合成密切相关，这一课题吸引了许多科学家的兴趣。虽然磁场本身被认为是一种非手性物理力，但磁场与其他物理力的组合使用有可能在没有任何光学活性化合物的情况下产生手性。在1.5 × 8 T的磁场中，以铜为催化剂，进行2-萘酚衍生物的氧化偶联反应，得到了光学活性小而明显的1，1 ′-联-2-萘酚衍生物。通过HPLC手性柱和/或产物的旋光度测定对映体过量。在磁场的作用下，手性的调控也在进一步的研究中，并考察了6-溴-2-萘酚与2-萘酚的交叉偶联反应。主要在自由基抑制剂的存在下获得所需的6-溴-1，1 ′-联-2-萘酚。

项目成果

Hiromichi Fujioka: "Optical Resolution of Racemic Norbornene Aldehydes : Kinetically Controlled Intramolecular Haloetherification of Ene Acetals"Tetrahedron Lett.. 41 (in press). (2000)

Hiromichi Fujioka：“外消旋降冰片烯醛的光学拆分：烯缩醛的动力学控制分子内卤醚化”Tetrahedron Lett.. 41（印刷中）。

H.Fujioka: "Optical Resolution of Racemic Norbornene Aldehydes : Kinetically Controlled Intramolecular Haloetherification of Ene Acetals"Tetrahedron Lett.. 41. 1829-1832 (2000)

H.Fujioka：“外消旋降冰片烯醛的光学拆分：烯乙缩醛的动力学控制分子内卤醚化”Tetrahedron Lett.. 41. 1829-1832 (2000)

Hiromichi Fujioka: "Asymmetric Desymmetrization of Saturated and unsaturated meso-1, 2-Diols"Tetrahedron. 56 (in press). (2000)

Hiromichi Fujioka：“饱和和不饱和内消旋 1, 2-二醇的不对称去对称化”四面体。

H.Fujioka: "Optical Resolution of Racemic Norbornene Aldehydes: Kinetically Controlled Intramolecular Haloetherification of Ene Acetals"Tetrahedron Lett.. 41. 1829-1832 (2000)

H.Fujioka：“外消旋降冰片烯醛的光学拆分：烯乙缩醛的动力学控制分子内卤醚化”Tetrahedron Lett.. 41. 1829-1832 (2000)

H.Fujioka: "Asymmetric Desymmetrization of Saturated and Unsaturated meso-1,2-Diols"Tetrahedron. 56. 10141-10151 (2000)

H.Fujioka：“饱和和不饱和内消旋-1,2-二醇的不对称去对称化”四面体。