Development and Application of Multifunctional Catalysts by Dynamic Stereochemical Control

由于自然界中手性的起源与绝对不对称合成密切相关，这一课题引起了许多科学家的极大兴趣。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产生手性，而不产生任何光活性化合物。将2-萘酚衍生物在1.5 ~ 8T的磁场下，在cu催化剂的存在下进行氧化偶联反应，得到了光学活性小但明显的1,1′-双-2-萘酚衍生物。通过HPLC手性柱和/或旋光法测定产物的对映体过量。对磁场作用下手性控制的进一步研究正在进行中。研究了6-溴-2-萘酚与2-萘酚的交叉偶联反应。期望的6-溴-1,1'-双-2-萘酚主要在自由基抑制剂存在的情况下得到。

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.