NSF-DFG Echem: CAS: Hydrofunctionalization of Alkenes by non-Redox Paired Electrocatalysis

在化学系化学催化项目的支持下，康奈尔大学的宋林与德国奥尔登堡卡尔·冯·奥西耶茨基大学的合作者一起，正在研究非氧化还原配对电催化对烯的对映选择性加氢功能化。LIN研究小组的目标是开发用于合成增值有机化合物的电催化工艺。这一研究计划的长期目标是促进可推广的电催化过程的发展或在合成化学中产生广泛的影响，并可能应用于新型药物、农用化学品和催化剂的构筑块的立体控制合成。许多这些重要的化合物含有碳-卤素和碳-碳键。这项研究的目标是建立高效、选择性和可持续的反应技术，利用丰富的原料化学品促进碳-卤素和碳-碳键的形成。电化学--一种直接利用电能驱动化学反应的过程--本质上是一种高效、选择性和可持续的技术。催化的引入可以进一步提高电化学反应的能量效率，并提供机会来控制最终产物的产率和同一性。该项目位于有机合成、催化和电化学的界面上。因此，它也非常适合各级科学家的教育。除了促进科学知识的进步和改进精细化工制造外，该项目还将通过研究和与德国团队的国际合作对学生的培训产生更广泛的影响。该项目由“NSF-DFG在电合成和电催化方面的领导机构活动(NSF-DFG eChem)”项目资助，这是一个由NSF和德国Forschungsgomeinschaft(DFG)参与的合作征集活动。康奈尔大学的宋林与德国奥尔登堡卡尔·冯·奥西耶茨基大学的合作者一起，正在开发用于烯烃加氢功能化的电催化方法。建议的研究将采用成对电解和氧化还原活性金属催化相结合的方法，以生成双催化中间体，以实现所需的氢功能化反应。将同时追求两个目标，包括(I)在盐化背景下建立非氧化还原配对电催化和(Ii)使用电分析和光谱工具对非氧化还原配对电催化进行机理研究。在获得初步的原理证明后，新的催化策略将进一步扩展到除盐化以外的其他类型的氢功能化反应。最后，LIN团队将开发一个电化学短期课程，旨在教育缺乏电化学经验的有机化学家，并为他们提供建立自己的电解实验所需的知识和指导。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Catalysis program in the Division of Chemistry, Song Lin of Cornell University is studying the enantioselective hydrofunctionalization of alkenes by non-redox paired electrocatalysis along with collaborators at Carl von Ossietzky University Oldenburg in Germany. The Lin research group aims to develop electrocatalytic processes for the synthesis of value-added organic compounds. The long-term objective of this research program is to facilitate the development of a generalizable electrocatalytic process or wide impact in synthetic chemistry, with possible application in the stereocontrolled synthesis of building blocks for new pharmaceuticals, agrochemicals, and catalysts. Many of these important compounds contain carbon-halogen and carbon-carbon bonds. The goal of this research is to establish efficient, selective, and sustainable reaction technologies that will promote the formation of carbon-halogen and carbon-carbon bonds using abundant feedstock chemicals. Electrochemistry—a process that directly uses electricity to drive chemical reactions—is an intrinsically efficient, selective, and sustainable technology. The introduction of catalysis can further augment the energy efficiency of electrochemical reactions and offer opportunities to 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. In addition to contributing to the advancement of scientific knowledge and improving fine chemical manufacturing, the project will also exert broader impacts on the training of students through research and international collaboration with the German team. The project is being funded through the "NSF-DFG Lead Agency Activity in Electrosynthesis and Electrocatalysis (NSF-DFG EChem)" opportunity, a collaborative solicitation that involves NSF and Deutsche Forschungsgemeinschaft (DFG).Together with collaborators at Carl von Ossietzky University Oldenburg in Germany, Song Lin of Cornell University is developing electrocatalytic methods for the hydrofunctionalization of alkenes. The proposed research will enlist the combination of paired electrolysis with redox-active metal catalysis to enable the generation of dual catalytic intermediates to achieve the desired hydrofunctionalization reactions. Two objectives will be pursued simultaneously, including (i) establishing non-redox paired electrocatalysis in the context of hydrochlorination and (ii) mechanistic investigation of non-redox paired electrocatalysis using electroanalytical and spectroscopic tools. Upon obtaining initial proof of principle, the new catalytic strategy will be further expanded to other types of hydrofunctionalization reactions beyond hydrochlorination. Finally, the Lin team will develop an electrochemical short course that aims to educate organic chemists with little electrochemistry experience and provide them with the knowledge and guidance needed to set up their own electrolysis experiments.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.