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.

化学部的化学合成计划由Song Lin教授支持该项目。 Song Lin教授是康奈尔大学化学与化学生物学系的教职员工。 Lin教授的实验室旨在开发用于建立包含碳氮键的有机分子的新方法。 碳氮键至关重要。超过85％的顶级药品至少具有一种碳氮键。考虑到这一点，进行的研究的目的是建立有效，选择性和可持续的反应技术，以促进丰富的起始材料的碳氮键形成。 电化学是一种直接使用电力来驱动化学反应的过程，是一种本质上有效，选择性和可持续的技术。这似乎是以可持续方式建立碳氮键的理想方法。但是，电化学反应通常无法提供完成特定转化所需的化学选择性和效率。可以控制过程的化学反应部分的催化引入可以解决此问题。这样一来，催化剂通过提供更好地控制最终产品的产量和身份的机会来提高电化学反应的能源效率。该项目在于有机合成，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。 林教授的小组通过将其研究的关键要素整合到大学和K-12级的下一代科学家的教育和培训中，从而积极从事外展活动。康奈尔大学的化学合成计划的资金是，康奈尔大学的化学合成计划的资金正在开发新的碳 - 氮基因构氮基质的电催化方法。拟议的研究促进了电化学和氧化还原活性金属催化的结合，作为一种可以使有机底物的高效和化学选择性胺化的一般方法。正在同时追求三个具体目标。正在研究烯烃用于合成的烷烃的电催化二氮氮杂的范围，烯烃用于合成氨基醇产品的烷烃的电化学氮杂二合剂正在进行，并且正在进行静电式范围，并进行了脱羧基和Deborylative Azidations azidations。额外的努力是研究使用动力学和伏安实验的电化学反应的机制。最后，正在采用新的反应方法来改善生物活性复合靶标的合成。 拟议的教育计划正在努力扩大国家对大学和K-12水平的STEM教育的基础设施，并特别着重于可持续性。 为了实现这一目标，林实验室正在积极参与与下一代科学标准一致的电气合成相关的教学模块的开发和颁布。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子优点和更广泛影响的审查标准来通过评估来通过评估来支持的。

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