Electrochemistry as an enabling tool for reaction discovery

电化学作为反应发现的有利工具

• 批准号: 10659868
• 负责人: Song Lin
• 金额: $ 34.96万
• 依托单位: CORNELL UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-20 至 2027-08-31
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/10659868
• 关键词: Address; Alcohols; Alkenes; Amines; Biomedical Research; Catalysis; Characteristics; Chemicals; Complex; Coupling; Development; Electrochemistry; Electrodes; Electrolyses; Funding; Goals; Grant; Hydrogen Bonding; Lead; Medicine; Metals; Methods; Modernization; Organic Chemistry; Organic Synthesis; Outcome; Oxidants; Oxidation-Reduction; Preparation; Process; Reaction; Reducing Agents; Research; Research Personnel; Side; Source; Speed; Structure; Techniques; Technology; Therapeutic Agents; Work; bioactive natural products; carboxylate; carboxylation; chemical bond; chemical synthesis; functional group; improved; innovation; insight; invention; meetings; novel; oxidation; pyridine; success; tool; trend; wasting

Project Summary This proposal focuses on using electrochemistry as an unconventional tool to uncover new organic reactions and invent synthetic strategies with the goal of facilitating the preparation of bioactive compounds. Improving the organic synthesis of medicinally active compounds is crucial to modern biomedical research. In this context, oxidation and reduction reactions are among the most important and frequently used processes in organic synthesis. However, manipulating the oxidation states of functional groups in complex settings with high efficiency, precision, and minimal waste remains an important challenge in modern organic chemistry. Given its many distinct characteristics, electrochemistry represents an attractive approach to discovering new reactivities, enabling new synthetic strategies, and meeting the prevailing trends in organic synthesis. Therefore, there exists a clear impetus for the invention of new reaction strategies to improve the scope of synthetic electrochemistry and provide new platforms for reaction discovery and synthetic innovations. In the past funding period, we demonstrated a new catalytic approach that combines electrochemistry and redox-metal catalysis for the oxidative difunctionalization of alkenes to access a diverse array of highly functionalized structures. These promising results led us to envision that electrochemistry will ultimately emerge as a powerful tool for solving a wide range of longstanding synthetic problems. In the new funding cycle, we aim to build upon our previous success but move our research into new grounds. In each of the projects targeted herein, we aim to apply electrochemistry to address a prominent challenge in organic synthesis. The transformations targeted in this grant are either currently unknown or display salient limitations in reaction scope or selectivity. Among the specific reactions that we aim to develop in the context of this grant are: two- and three-component cross-electrophile couplings; asymmetric synthesis and late-stage functionalization of N-containing compounds; and regioselective C–H functionalization of pyridines. In addition, in-depth studies using canonical physical organic and electroanalytical techniques will provide insights into the reaction mechanisms. The development and mechanistic understanding of these proposed transformations will represent significant advances for the field of organic synthesis.

项目概要 该提案的重点是使用电化学作为非常规工具来发现新的有机化合物 反应并发明合成策略，以促进生物活性物质的制备 改善药物活性化合物的有机合成对于现代至关重要。 在这方面，氧化和还原反应是最重要和最重要的。 然而，有机合成中经常使用的过程是操纵官能团的氧化态。 在复杂环境中高效、精确、最少浪费的群体仍然是一个重要的因素 鉴于电化学的许多独特特征，现代有机化学面临的挑战。 代表了一种发现新反应性、实现新合成策略的有吸引力的方法，并且 符合有机合成的流行趋势，因此存在明显的推动力。 发明新的反应策略，以扩大合成电化学的范围并提供新的 在过去的资助期间，我们展示了反应发现和合成创新的平台。 一种结合电化学和氧化还原金属催化的新催化方法 烯烃的双官能化以获得多种高度官能化的结构。 有希望的结果使我们设想电化学最终将成为一种强大的工具 在新的融资周期中，我们的目标是解决一系列长期存在的综合问题。 我们以前的成功，但将我们的研究转移到新的领域，在此针对的每个项目中， 我们的目标是应用电化学来解决有机合成中的突出挑战。 本次资助的目标转化要么目前未知，要么表现出明显的反应局限性 我们旨在在这笔赠款的背景下制定的具体反应包括： 二元和三元交叉亲电子偶联；不对称合成和后期 含氮化合物的官能化；以及吡啶的区域选择性C-H官能化。 此外，使用规范的物理有机和电分析技术进行深入研究将提供 对这些反应机制的发展和机理的理解。 拟议的转变将代表有机合成领域的重大进步。

项目成果

Electrocatalysis as an enabling technology for organic synthesis.

• DOI: 10.1039/d1cs00223f
• 发表时间: 2021-07-21
• 期刊: Chemical Society reviews
• 影响因子: 46.2
• 作者: Novaes LFT ;Liu J ;Shen Y ;Lu L ;Meinhardt JM ;Lin S
• 通讯作者: Lin S

A tutorial on asymmetric electrocatalysis.

• DOI: 10.1039/d3cs00511a
• 发表时间: 2023-11
• 期刊: Chemical Society reviews
• 影响因子: 46.2
• 作者: J. Rein;Samson B Zacate;Kaining Mao;Song Lin

Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols.

• DOI: 10.1002/anie.201910300
• 发表时间: 2019-11
• 期刊: Angewandte Chemie
• 作者: W. Zhang;K. Carpenter;Song Lin

Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism.

• DOI: 10.1021/jacs.0c08532
• 发表时间: 2020-12-09
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Zhang W;Lin S
• 通讯作者: Lin S

Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor.

使用标准化微型反应器释放电化学高通量实验的潜力。

• DOI: 10.1021/acscentsci.1c00328
• 发表时间: 2021-08-25
• 期刊: ACS central science
• 影响因子: 18.2
• 作者: Rein J;Annand JR;Wismer MK;Fu J;Siu JC;Klapars A;Strotman NA;Kalyani D;Lehnherr D;Lin S
• 通讯作者: Lin S