CAREER: Catalytic Electrochemical Amination Reactions

职业：催化电化学胺化反应

• 批准号: 1751839
• 负责人: Song Lin
• 金额: $ 65万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-05-01 至 2023-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1751839&HistoricalAwards=false
• 关键词: CAREER; Catalytic; Electrochemical; Amination; Reactions

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Song Lin. Professor Song Lin is a faculty member in the Department of Chemistry and Chemical Biology at Cornell University. Prof. Lin's lab aims to develop new methods for building organic molecules that contain carbon-nitrogen bonds. Carbon-nitrogen bonds are critically important. Over 85% of the top-selling pharmaceuticals have at least one carbon-nitrogen bond. With this in mind, the goal of the research being pursued is to establish efficient, selective, and sustainable reaction technologies that will promote the formation of carbon-nitrogen bonds from abundant starting materials. Electrochemistry, a process that directly uses electricity to drive chemical reactions, is an intrinsically efficient, selective, and sustainable technology. It would appear to be an ideal method for making carbon-nitrogen bonds in a sustainable manner. However, electrochemical reactions frequently do not afford the chemical selectivity and efficiency necessary to accomplish a particular transformation. The introduction of catalysis that can control the chemical reaction portion of the process can solve this problem. In so doing, the catalyst augments the energy efficiency of electrochemical reactions by offering an opportunity to better control the yield and identity of the end product. The project lies at the interface of organic synthesis, catalysis, and electrochemistry. Therefore, it is also well suited for the education of scientists at all levels. Prof. Lin's group is actively engaged in outreach activities by integrating the key elements of their research into the education and training of the next generation of scientists at both collegiate and K-12 levels.With funding from the Chemical Synthesis Program of the Chemistry Division, Prof. Lin of Cornell University is developing electrocatalytic methods for new carbon-nitrogen coupling reactions. The proposed research enlists the combination of electrochemistry and redox-active metal catalysis as a general approach to enable highly efficient and chemoselective amination of organic substrates. Three specific aims are being pursued simultaneously. The scope of the electrocatalytic diazidation of alkenes for the synthesis of vicinal diamines is being investigated, the electrochemical azidooxygenation of alkenes for the synthesis of aminoalcohol products is being advanced, and an electrocatalytic paradigm to decarboxylative and deborylative azidations is being expanded. Additional efforts are studying the mechanisms of the electrochemical reactions using kinetic and voltammetric experiments. Finally, the new reaction methods are being employed to improve the synthesis of bioactive complex targets. The proposed educational plan is working to expand the nation's infrastructure for STEM education on collegiate and K-12 levels with a particular emphasis on sustainability. Toward this goal, the Lin Lab is actively participating in the development and promulgation of electrosynthesis-related teaching modules aligned with the Next Generation Science Standards.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

化学系的化学合成项目支持宋林教授的项目。宋林教授是康奈尔大学化学与化学生物学系的教员。 林教授的实验室旨在开发构建含有碳氮键的有机分子的新方法。 碳-氮键至关重要。超过85%的畅销药物至少有一个碳氮键。考虑到这一点，正在进行的研究的目标是建立高效，选择性和可持续的反应技术，这将促进从丰富的起始材料形成碳-氮键。 电化学是一种直接使用电力来驱动化学反应的过程，是一种本质上高效，选择性和可持续的技术。这似乎是一种以可持续的方式制造碳氮键的理想方法。然而，电化学反应通常不能提供完成特定转化所必需的化学选择性和效率。引入可以控制该过程的化学反应部分的催化剂可以解决这个问题。这样，催化剂通过提供更好地控制最终产物的产率和特性的机会来提高电化学反应的能量效率。该项目位于有机合成，催化和电化学的界面。因此，它也非常适合各级科学家的教育。 林教授的研究小组积极参与外展活动，将研究的关键元素融入大学和K-12水平的下一代科学家的教育和培训中。康奈尔大学的林教授在化学部化学合成计划的资助下，正在开发新的碳氮偶联反应的电催化方法。拟议的研究将电化学和氧化还原活性金属催化的组合作为一种通用方法，以实现有机底物的高效和化学选择性胺化。三个具体目标正在同时实现。烯烃的电催化叠氮化合成邻二胺的范围正在研究中，烯烃的电化学叠氮氧化合成氨基醇产品的研究正在推进，脱羧和脱硼叠氮化的电催化范例正在扩展。另外的努力是使用动力学和伏安实验研究电化学反应的机制。最后，新的反应方法正在被用于改进生物活性复合物靶标的合成。 拟议的教育计划正在努力扩大国家在大学和K-12水平上的STEM教育基础设施，特别强调可持续性。 为此，Lin实验室积极参与了符合下一代科学标准的电合成相关教学模块的开发和颁布。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估而被认为值得支持。

项目成果

A general, electrocatalytic approach to the synthesis of vicinal diamines

• DOI: 10.1038/s41596-018-0010-0
• 发表时间: 2018-08-01
• 期刊: NATURE PROTOCOLS
• 影响因子: 14.8
• 作者: Fu, Niankai;Sauer, Gregory S.;Lin, Song
• 通讯作者: Lin, Song

Eight-Fold Intensification of Electrochemical Azidooxygenation with a Flow-Through Electrode

• DOI: 10.1021/acssuschemeng.2c01525
• 发表时间: 2022-06-13
• 期刊: ACS SUSTAINABLE CHEMISTRY & ENGINEERING
• 影响因子: 8.4
• 作者: Guo, Shichen;Kim, Myung Jun;Wiley, Benjamin J.
• 通讯作者: Wiley, Benjamin J.

Recent Advances in Titanium Radical Redox Catalysis

• DOI: 10.1021/acs.joc.9b02465
• 发表时间: 2019-11-15
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: McCallum, Terry;Wu, Xiangyu;Lin, Song
• 通讯作者: Lin, Song

Electrocatalytic Diazidation of Alkenes

烯烃的电催化二叠氮化

• DOI: 10.1016/j.trechm.2019.10.005
• 发表时间: 2020
• 期刊: Trends in Chemistry
• 影响因子: 15.7
• 作者: Novaes, Luiz F.T.;Lin, Song
• 通讯作者: Lin, Song

Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors

• DOI: 10.1021/acscatal.2c05186
• 发表时间: 2022-11
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Luiz F. T. Novaes;Yi Wang;Jinjian Liu;Xavier Riart-Ferrer;Wan-Chen Cindy Lee;Niankai Fu;J. S. Ho;X. Zhang;Song Lin