享有特权的氨酸基金属有机框架用于广泛的非对称催化剂
Joseph M Falkowski1, Takahiro Sawano, Teng Zhang
1Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|April 2, 2014
概括
研究人员开发了BINAP金属有机框架 (MOF) 作为强大的,enantioselective催化剂. 这些用Rh或Ru功能化的固体位点催化剂在关键的有机转化中表现出高的选择性和活性.
科学领域:
- 材料科学 材料科学 材料科学
- 催化剂是一种催化剂.
- 有机化学 有机化学
背景情况:
- 金属有机框架 (MOF) 为催化提供可调节的多孔结构.
- 在以MOF为基础的催化剂中实现高反选择性仍然是一个挑战.
- 合成后的修改允许在预制MOF中引入活性金属位点.
研究的目的:
- 通过使用BINAP衍生链接器 (BINAP-MOF) 合成一种强大的基于Zr的MOF.
- 用Ru和Rh复合物用BINAP-MOF进行后合成金属化.
- 评估这些功能化MOF在不对称的有机转换中的催化性能.
主要方法:
- 基于Zr的金属有机框架 (MOF) 与由BINAP衍生的二碳酸盐链接剂的合成.
- MOF的合成后化与 (Ru) 和 (Rh) 复合物.
- 进行X射线吸收细结构 (XAFS) 研究,以描述金属协调环境.
- 在不对称的加和化反应中测试催化活性和酶选择性.
主要成果:
- 合成的BINAP-MOF具有坚固性和多孔性.
- 具有Rh功能化的BINAP-MOF表现出高反选择性 (高达99% ee) 和比同质催化剂高3倍的活性.
- 含有Ru功能化的BINAP-MOF含有Ru-BINAP预催化剂,其协调环境与同质类型相似.
- 催化剂有效地调解了不对称的添加和化.
结论:
- 合成后金属化BINAP-MOF作为多功能单位固体催化剂.
- 这些以MOF为基础的催化剂对各种不对称的有机反应表现出极好的反选择性和活性.
- 开发的MOF催化剂在重要的有机合成中,为同质催化剂提供了一个有希望的替代品.
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