New Lewis Bases for Chemical Catalysis

用于化学催化的新路易斯碱

• 批准号: 1665141
• 负责人: Karl Scheidt
• 金额: $ 45万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665141&HistoricalAwards=false
• 关键词: New; Lewis; Bases; Chemical; Catalysis

New Lewis Bases for Chemical CatalysisThe Chemical Synthesis Program of the Chemistry Division supports the project by Professor Karl Scheidt. Professor Scheidt is a faculty member in the Department of Chemistry at Northwestern University. He is developing new classes of chemical catalysts. Chemical catalysts enable the efficient and sustainable synthesis of new small molecules and materials that are important for pharmaceutical, material science, and biomedical research communities. Because of their utility in these areas, catalysts derived from Lewis bases (molecules capable of donating an electron pair), and in particular N-heterocyclic carbenes (NHCs), have been of particular interest, and work with these systems has exploded during the last decade. In this effort, NHCs have frequently been employed as ligands to generate chiral metal complexes as well as catalysts in their own right in the absence of a transition metal (metal free or organocatalysis). Yet in spite of this effort, little is known about how NHC-based catalysts can be tuned in order to optimize their performance in new classes of reactions. For this reason, the Scheidt group is exploring a novel family of NHC-transition metal complexes as catalysts. These new systems can be used to systematically study how changes in structure alter the properties and catalytic behavior of the NHC. The work has broad implications for how new catalysts in the NHC-family will be designed in the future. The project lies at the intersection of organic, asymmetric synthesis, and catalysis and thus is excellent for training and education in interdisciplinary science. In terms of broader impacts of the project, Dr. Scheidt is actively engaged in outreach activities focused on underrepresented group recruitment into the STEM fields.The sustainability and advancement of society relies on new discoveries based on molecular science. One such discovery is the general utility of new electron-rich molecules (Lewis bases) as catalysts for a broad range of reactions, many of which have implications for materials, biological, and pharmacological efforts. In the specific work being pursued, Dr. Scheidt is using a novel family of N-heterocyclic carbine (NHC)-metal complexes to both catalyze new asymmetric bond forming reactions and to provide new mechanistic insights into how the nucleophilicity of an NHC-catalyst can be tuned. The specific synthetic targets selected for the effort are alpha-boryl amines. Since there are major limitations to the currently available methods for alpha-borylation reactions that have hampered the use of the chosen targets as synthetic building blocks, the choice of the alpha boryl amines as targets nicely highlights the broad synthetic implications of the catalysts being developed. The mechanistic insights being gained center on advancing our knowledge of Lewis base and transition metal catalysis and determining the structure-reactivity relationships that govern catalyst behavior. Dr. Scheidt's outreach activities build on his research and target the improved recruitment of underrepresented groups into the chemistry doctoral program at Northwestern University.

化学催化的新路易斯碱化学部的化学合成计划支持Karl Scheidt教授的项目。 Scheidt 教授是西北大学化学系的教员。他正在开发新型化学催化剂。化学催化剂能够高效、可持续地合成新的小分子和材料，这对于制药、材料科学和生物医学研究界非常重要。由于它们在这些领域的实用性，源自路易斯碱（能够提供电子对的分子）的催化剂，特别是 N-杂环卡宾 (NHC)，一直受到特别关注，并且在过去的几年里，这些系统的研究呈爆炸式增长。十年。在这项工作中，NHC 经常被用作配体来生成手性金属配合物以及在没有过渡金属（无金属或有机催化）的情况下本身的催化剂。然而，尽管做出了这些努力，人们对于如何调整基于 NHC 的催化剂以优化其在新类型反应中的性能仍知之甚少。为此，Scheidt 团队正在探索一种新型 NHC-过渡金属配合物家族作为催化剂。这些新系统可用于系统地研究结构变化如何改变 NHC 的特性和催化行为。这项工作对于未来如何设计 NHC 系列中的新催化剂具有广泛的影响。该项目位于有机、不对称合成和催化的交叉点，因此非常适合跨学科科学的培训和教育。就该项目更广泛的影响而言，Scheidt 博士积极参与外展活动，重点招募代表性不足的群体进入 STEM 领域。社会的可持续性和进步依赖于基于分子科学的新发现。其中一项发现是新的富电子分子（路易斯碱）作为广泛反应的催化剂的普遍用途，其中许多反应对材料、生物和药理学工作具有影响。在正在进行的具体工作中，Scheidt 博士正在使用一种新型 N-杂环卡宾 (NHC)-金属配合物家族来催化新的不对称键形成反应，并为 NHC 催化剂的亲核性如何发挥作用提供新的机制见解。调整一下。为这项工作选择的具体合成目标是α-硼基胺。由于目前可用的α-硼基化反应方法存在重大限制，阻碍了所选目标作为合成结构单元的使用，因此选择α硼基胺作为目标很好地突出了正在开发的催化剂的广泛合成意义。所获得的机理见解集中于推进我们对路易斯碱和过渡金属催化的了解，并确定控制催化剂行为的结构-反应性关系。沙伊特博士的外展活动以他的研究为基础，旨在改善西北大学化学博士项目中代表性不足群体的招募情况。

项目成果

Development of Ferrocene-Based Planar Chiral Imidazopyridinium Salts for Catalysis

用于催化的二茂铁基平面手性咪唑并吡啶鎓盐的开发

• DOI: 10.1021/acs.organomet.0c00312
• 发表时间: 2020-06-30
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Keegan P. Fitzpatrick;C. Schwamb;Christopher T. Check;K. Jang;David N. Barsoum;K. Scheidt
• 通讯作者: K. Scheidt

Enantioselective Synthesis of α-Amidoboronates Catalyzed by Planar-Chiral NHC-Cu(I) Complexes

平面手性 NHC-Cu(I) 配合物催化对映选择性合成 α-氨基硼酸酯

• DOI: 10.1021/jacs.8b05045
• 发表时间: 2018-07
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Schwamb, C. Benjamin;Fitzpatrick, Keegan P.;Brueckner, Alexander C.;Richardson, H. Camille;Cheong, Paul H.;Scheidt, Karl A.
• 通讯作者: Scheidt, Karl A.

Enantioselective Copper-Catalyzed Borylative Amidation of Allenes

铜催化的烯对映选择性硼化酰胺化

• DOI: 10.1021/jacs.2c10507
• 发表时间: 2022-12
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Byun, Seunghwan;Farah, Abdikani Omar;Wise, Henry R.;Katchmar, Andrew;Cheong, Paul H.;Scheidt, Karl A.
• 通讯作者: Scheidt, Karl A.