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; 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.

项目摘要 该建议重点是使用电化学作为一种非常规的工具来发现新的有机物 反应和发明合成策略，目的是促进生物活性的准备 化合物。改善药物活性化合物的有机合成对现代至关重要 生物医学研究。在这种情况下，氧化和减少反应是最重要的， 有机合成中经常使用的过程。但是，操纵功能的氧化态 具有高效率，精度和最小废物的复杂环境中的小组仍然是重要的 现代有机化学的挑战。鉴于其许多独特的特征，电化学 代表了发现新的反应率，实现新的合成策略的吸引人的方法，并 满足有机合成的普遍趋势。因此，存在明显的动力 新反应策略的发明以提高合成电化学范围并提供新的反应策略 反应发现和合成创新的平台。在过去的资金期间，我们证明了 一种新的催化方法，结合了氧化的电化学和氧化还原 - 金属催化 烷烃的扩展化以获取高度功能化结构的潜水员阵列。这些 有希望的结果使我们设想电化学最终将成为有力的工具 解决各种长期的合成问题。在新的资金周期中，我们的目标是建立 我们以前的成功，但将我们的研究转化为新的理由。在本文针对的每个项目中， 我们旨在应用电化学来应对有机综合中的巨大挑战。这 该赠款中针对的转换目前是未知的，或者在反应中显示出明显的限制 范围或选择性。我们旨在在这笔赠款背景下发展的具体反应包括： 两分和三分量的跨电动耦合；不对称合成和晚期 含N的化合物的功能化；和吡啶的调节性C – H功能化。在 另外，使用规范物理有机和电分析技术的深入研究将提供 洞察反应机制。这些对这些的发展和机械理解 提出的转化将代表有机合成领域的重大进展。