Chiral Porous Metal-Organic Frameworks as A Tunable Platform for Asymmetric Catalysis

手性多孔金属有机框架作为不对称催化的可调平台

• 批准号: 1464941
• 负责人: Wenbin Lin
• 金额: $ 64万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-06-15 至 2019-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464941&HistoricalAwards=false
• 关键词: Chiral; Porous; Metal; Organic; Frameworks

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Wenbin Lin at the University of Chicago is developing new types of solid catalysts that translate solution phase catalysis into the solid phase. The production of most commodity chemicals utilizes solid phase catalysts due to their efficiency in chemical usage and separation. Certain important chemicals presently are only made in solutions because solid phase catalysts for their synthesis are not known. These processes usually require lots of organic solvents and can be quite wasteful. In this research project Professor Lin is synthesizing new classes of solid phase catalysts based upon metal-organic frameworks (MOFs), materials that are built from organic molecules and the framework pieces and metal atoms as the connecting points. The materials are porous which enables molecules to move in and out of the structures, and by tailoring the metal atom connection sites, the researchers are dictating the types of catalysis that can occur within the material. By matching the structures of the metal atom sites to known solution phase catalysts, the researchers are creating MOFs that can perform the analogous solution phase reactions. The project is also integrating research, training and education. Graduate and undergraduate students participating in the research project are learning important research and communication skills. Professor Lin is also partnering with the Collegiate Partner Program to host Chicago area high school students for a research experience in the laboratory.Professor Lin is developing strategies to synthesize novel chiral MOFs based upon m-BINAP motifs with large open channels and pores and to study their activity as single-site solid catalysts for asymmetric catalytic reactions. The studies are focusing on: 1) tuning the effective reaction space of chiral, porous MOFs through the inclusion of mixed linkers; 2) exploring earth-abundant metal asymmetric catalysis and organocatalysis within the MOFs; 3) realizing asymmetric photocatalysis via photoactive multicomponent MOF assemblies; and 4) developing multifunctional MOF systems for asymmetric tandem catalysis. The ability to determine MOF structures precisely provides distinct advantages over many other types of heterogeneous asymmetric catalysts, because the catalytic activities/selectivities of the MOF can be approximated using a range of characterization methods and altered through the use of tailor-made building blocks. MOF-based single-site solid asymmetric catalysts have the potential to become cost-competitive heterogeneous catalysts and find application in fine chemical synthesis.

在这个由化学系化学催化计划资助的项目中，芝加哥大学的林文斌教授正在开发新型固体催化剂，将溶液相催化转化为固相催化。 由于固相催化剂在化学品使用和分离方面的效率，大多数商品化学品的生产使用固相催化剂。 某些重要的化学品目前仅在溶液中制备，因为用于其合成的固相催化剂是未知的。这些方法通常需要大量的有机溶剂，并且可能相当浪费。 在这个研究项目中，林教授正在合成基于金属有机框架（MOFs）的新型固相催化剂，这些材料是由有机分子和框架碎片以及金属原子作为连接点构建的。 这些材料是多孔的，使分子能够进出结构，通过调整金属原子连接位点，研究人员正在决定材料中可能发生的催化类型。 通过将金属原子位点的结构与已知的溶液相催化剂相匹配，研究人员正在创建可以进行类似溶液相反应的MOF。 该项目还整合了研究、培训和教育。参加研究项目的研究生和本科生正在学习重要的研究和沟通技巧。 此外，林教授还与美国大学生合作伙伴计划（Collegiate Partner Program）合作，邀请芝加哥地区的高中生在实验室进行研究。林教授正在开发基于m-BINAP基序的新型手性MOFs的合成策略，并研究其作为单中心固体催化剂在不对称催化反应中的活性。研究重点是：1）通过包含混合连接体来调整手性多孔MOF的有效反应空间; 2）探索MOF内地球上丰富的金属不对称催化和有机催化; 3）通过光活性多组分MOF组装体实现不对称重排;以及4）开发用于不对称串联催化的多功能MOF系统。与许多其他类型的非均相不对称催化剂相比，精确确定MOF结构的能力具有明显的优势，因为可以使用一系列表征方法来近似MOF的催化活性/选择性，并通过使用定制的构建块来改变。 基于MOF的单活性中心固体不对称催化剂有可能成为具有成本竞争力的多相催化剂，并在精细化学合成中得到应用。