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

化学系化学催化项目为新墨西哥大学（UNM） Ramesh Giri教授的研究提供了这项职业奖。本研究的目的是利用地球上丰富且廉价的铜（Cu）作为催化剂，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，为合成复杂和多样化的分子（如药物和有机材料）提供了强大的工具。本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的新方案，对社会产生了积极的影响。Giri教授与新墨西哥大学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一个外展计划。将交叉耦合集成到串联和多组分（MC）反应歧管中有可能创造新的合成方法。研究的重点是开发铜化合物作为所提出的转化的可持续催化剂。作为教育组成部分的一部分，研究者为高年级本科生和研究生开发了一门课程，专注于有机金属化学，强调在开发新的化学转化过程中可持续过渡金属的使用。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，以增加跨碳-碳多键（烯烃、炔和烯），随后以串联方式与有机卤化物交叉偶联。铜避免β -氢化物消除的能力有望促进含有β -氢的亲电试剂和亲核试剂的串联和MC交叉偶联。杂化双齿配体包含pi-受体和sigma-给体基团，用于生成+1氧化态的稳定活性Cu，以进行所提出的转化。配体经过立体和电子调谐，使铜对反应性较弱的芳基卤化物具有反应性。另外，基于有机电子供体的有机催化剂通过单电子转移过程与有机卤化物反应，为与活性较低的芳基卤化物偶联反应提供了另一种策略。该项目的长期目标是使用手性非外消旋配体对映选择性地进行反应，以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，为从高中到研究生培养未来的科学家提供了机会。该奖项还支持Giri小组的推广工作，培训来自传统上代表性不足的科学群体的高中生和本科生。

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.