CAREER: SusChEM: Development of Tandem and Multi-Component Couplings with Base Metals and Organic Electron Donors

职业：SusChEM：使用贱金属和有机电子给体开发串联和多组分耦合

• 批准号: 2002846
• 负责人: Ramesh Giri
• 金额: $ 23.48万
• 依托单位: Pennsylvania State Univ University Park
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2022-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2002846&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Development; Tandem; Multi

With this CAREER Award, the Chemical Catalysis program of the Division of Chemistry is supporting the research of Professor Ramesh Giri of the University of New Mexico (UNM). The goal of this research is the development of catalytic chemical reactions using the earth-abundant and inexpensive copper (Cu) as the catalyst. The target reactions provide powerful tools for the syntheses of complex and diversified molecules, such as drugs and organic materials, by limiting the required number of reaction steps and thus minimizing the time for process development. The outcomes of this investigation have a positive impact on society by developing novel protocols for organic chemical transformations based on earth-abundant, sustainable catalysts. Professor Giri has established a partnership with the UNM College Enrichment and Outreach Program to involve undergraduates from traditionally underrepresented groups. He has established an outreach program with the South Valley Academy, a public charter school in Benalillo County, New Mexico. Integration of cross-coupling into the tandem and multi-component (MC) reaction manifolds has the potential to create new synthetic methodologies. The research focuses on developing Cu compounds as sustainable catalysts for the proposed transformations. As part of the education component, the investigator has developed a course for senior undergraduates and graduate students focused on organometallic chemistry that emphasizes the use of sustainable transition metals in the development of new chemical transformations. In this project, various organometallic reagents, amines, alcohols, and carbonyl compounds are employed as sources of nucleophiles to add across carbon-carbon multiple bonds (olefins, alkynes, and allenes) and subsequently cross-couple with organohalides in a tandem fashion. The ability of copper to avoid beta-hydride eliminations is expected to facilitate the tandem and MC cross-couplings of electrophiles and nucleophiles that contain beta-hydrogens. Hybrid bidentate ligands containing both pi-acceptor and sigma-donor groups are employed to generate stable and active Cu in the +1 oxidation state required to conduct the proposed transformations. The ligands are tuned sterically and electronically to render Cu reactive towards the less reactive aryl halides. Alternatively, organic electron donor-based organic catalysts, which react with organohalides via a single electron transfer process, provide an alternative strategy for coupling reactions with less reactive aryl halides. A long-term goal of the project is to perform the reactions enantioselectively using chiral, non-racemic ligands to prepare complex molecules with multiple chiral centers.The research is performed at the interface of organic, inorganic and organometallic chemistry, which provides an opportunity for training future scientists from high school to graduate school. This award also supports the outreach efforts of the Giri group to train high school and undergraduate students from traditionally underrepresented groups in the sciences.

有了这个职业奖，化学系的化学催化计划正在支持新墨西哥州（UNM）大学的Ramesh Giri教授的研究。本研究的目的是开发使用地球上丰富且廉价的铜（Cu）作为催化剂的催化化学反应。靶向反应通过限制所需的反应步骤数量，从而最大限度地减少工艺开发时间，为复杂和多样化分子（如药物和有机材料）的合成提供了有力的工具。这项调查的结果通过开发基于地球丰富的可持续催化剂的有机化学转化新方案，对社会产生了积极影响。吉里教授已经建立了与UNM大学丰富和推广计划的合作伙伴关系，从传统上代表性不足的群体涉及本科生。 他与新墨西哥州贝纳里洛县的一所公立特许学校南谷学院建立了一个外展项目。将交叉耦合集成到串联和多组分（MC）反应歧管中具有创造新的合成方法的潜力。该研究的重点是开发铜化合物作为可持续的催化剂，用于拟议的转换。作为教育部分的一部分，研究员为高年级本科生和研究生开发了一门课程，重点是有机金属化学，强调在开发新的化学转化过程中使用可持续的过渡金属。在这个项目中，各种有机金属试剂，胺，醇和羰基化合物被用作亲核试剂的来源，以添加跨碳-碳多重键（烯烃，炔和联烯），并随后以串联方式与有机卤化物交叉偶联。预期铜避免β-氢化物消除的能力促进含有β-氢的亲电试剂和亲核试剂的串联和MC交叉偶联。采用含有π-受体和σ-供体基团的混合双齿配体来产生进行所提出的转化所需的+1氧化态的稳定和活性Cu。的配体的空间和电子调谐，使铜反应对反应性较低的芳基卤化物。或者，基于有机电子给体的有机催化剂，其通过单电子转移过程与有机卤化物反应，提供了与反应性较低的芳基卤化物进行偶联反应的替代策略。该项目的长期目标是使用手性、非外消旋配体进行对映选择性反应，制备具有多个手性中心的复杂分子。该研究在有机、无机和有机金属化学的界面上进行，为培养从高中到研究生的未来科学家提供了机会。该奖项还支持Giri集团的外联工作，以培训传统上代表性不足的科学群体的高中和本科生。