在不对称的催化过程中,螺旋三基单酸盐作为连接体
Manfred T Reetz1, Hongchao Guo, Jun-An Ma
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany. reetz@mpi-muelheim.mpg.de
Journal of the American Chemical Society
|March 3, 2009
概括
合成了具有螺旋结构的新的性三基酸连接物. 这些体积庞大的配体在不对称的化反应中达到高的反选择性,证明了它们在催化中的潜力.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 连接体设计 连接体设计
背景情况:
- 基拉尔连接体对于对抗选择性合成至关重要.
- 开发新的联结体架构可以提高催化效率和选择性.
- 连接体中的螺旋结构可以传递独特的立体化学控制.
研究的目的:
- 合成和表征一种新家族的奇拉性,C(3) - 对称的单酸连接体.
- 为了研究体体积和形状刚度对连接体性能的影响.
- 评估这些新型配体在Rh催化不对称化中的有效性.
主要方法:
- 两步合成,涉及性二醇 (BINOL) 的单化,其次是酸化.
- 使用X射线晶体学和NMR光谱学进行表征.
- 在同质醇的Rh催化不对称化中作为配体的应用.
主要成果:
- 成功制备了新的螺旋式C(3) - 对称的单酸盐配体.
- 由亚达曼坦衍生而来的最受硬质阻碍的连接体采用了状几何形状和定义的螺旋性.
- 这些庞大的螺旋连体在不对称化中实现了高的反选择性 (79-98% ee).
- 不那么刚硬的类型表现出形状灵活性,并导致较差的酶选择性 (32% ee).
结论:
- 来自BINOL的大型,形状刚性螺旋式酸连接物对不对称化有效.
- 连接体的形状灵活性会对酶选择性产生负面影响.
- 合成的连接体代表了一种有前途的新类别,用于性催化.
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