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: 1554299
• 负责人: Ramesh Giri
• 金额: $ 67.5万
• 依托单位: University of New Mexico
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-04-01 至 2020-02-29
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1554299&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.

凭借这一职业奖，化学系的化学催化项目正在支持新墨西哥大学 (UNM) 拉梅什·吉里 (Ramesh Giri) 教授的研究。这项研究的目标是利用地球上丰富且廉价的铜（Cu）作为催化剂来开发催化化学反应。目标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，为合成复杂且多样化的分子（例如药物和有机材料）提供了强大的工具。这项研究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，对社会产生积极影响。吉里教授与新墨西哥大学学院强化和外展计划建立了合作伙伴关系，让来自传统上代表性不足群体的本科生参与进来。 他与新墨西哥州贝纳利洛县的一所公立特许学校南谷学院建立了外展计划。将交叉偶联集成到串联和多组分（MC）反应歧管中具有创建新合成方法的潜力。该研究的重点是开发铜化合物作为拟议转化的可持续催化剂。作为教育部分的一部分，研究人员为高年级本科生和研究生开发了一门课程，重点关注有机金属化学，强调在开发新的化学转化过程中使用可持续过渡金属。在该项目中，采用各种有机金属试剂、胺、醇和羰基化合物作为亲核试剂来源，以跨碳-碳多重键（烯烃、炔烃和丙二烯）加成，然后以串联方式与有机卤化物交叉偶联。铜避免β-氢消除的能力预计将促进含有β-氢的亲电子试剂和亲核试剂的串联和MC交叉偶联。含有 pi 受体和 sigma 供体基团的杂化二齿配体用于生成进行所提出的转化所需的 +1 氧化态的稳定且活性的 Cu。配体在空间和电子上进行调整，使铜对反应性较低的芳基卤化物具有反应性。或者，基于有机电子给体的有机催化剂通过单一电子转移过程与有机卤化物反应，为与反应性较低的芳基卤化物的偶联反应提供了另一种策略。该项目的长期目标是利用手性、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 集团的外展工作，以培训来自传统科学领域代表性不足群体的高中生和本科生。