Hybrid Electrochemically-paired Light Irradiated Organic Synthesis (Acronym: HELIOS)

混合电化学配对光照射有机合成（缩写：HELIOS）

• 批准号: EP/Y037413/1
• 负责人: Joshua Barham
• 金额: $ 161.86万
• 依托单位: University of Strathclyde
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2024
• 资助国家: 英国
• 起止时间: 2024 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FY037413%2F1
• 关键词: Hybrid; Electrochemically; paired; Light; Irradiated

The synergy of visible light and electrical energy has been employed for decades in water splitting to hydrogen, but only recently was used to power the synthesis of higher value complex organic molecules (natural products, pharmaceuticals). Synthetic photoelectrochemistry (PEC) is receiving notable attention due to its enhanced scope of redox transformations, sustainability, and selectivity compared to photo- or electrochemistry alone. Synthetic electrochemistry (EC) is a useful synthetic tool that replaces atom uneconomical chemical redox agents with simple electrons and protons. However, in most EC reactions and in all PEC reactions, only one half-reaction of the cell is optimized to generate value; the other half-reaction sacrifices its own electrode or redox additives. 'Paired' electrolysis, where both half-reactions afford useful species, is key to sustainability and efficiency.HELIOS will discover, develop and disseminate paired synthetic PEC reactions. Intermediates generated by both half-reactions are converged in novel, creative chemical transformations, including:i) marriage of radicals or ions generated by each half-reaction to furnish phenethylamines and azetidines, valued pharmaceuticalsii) ring-fusing reactions that furnish bicyclic scaffolds, toward molecules with high 3D character urgently required in drug discoveryiii) alcohol inversion reactions that are catalytic, environmentally-friendly and use mild conditions'Multifunctional' catalysts will be used that can be electro-activated in both cathodic and anodic half-cells, to photochemically generate and stabilize reactive intermediates.HELIOS i) harnesses electrical and light energy to rapidly convert cheap, abundant chemical feedstocks to value-added complex molecules and ii) improves the sustainability and selectivity of synthetic PEC and EC processes. HELIOS opens an entirely new dimension of chemical reactivity that will revolutionize the way chemists use redox to synthesize molecules.

几十年来，可见光和电能的协同作用一直用于水分解为氢，但直到最近才用于合成更高价值的复杂有机分子（天然产物，药物）。合成光电化学（PEC）由于其与光化学或电化学相比增强的氧化还原转化范围，可持续性和选择性而受到显着关注。合成电化学（EC）是一种有用的合成工具，它用简单的电子和质子取代原子不经济的化学氧化还原剂。然而，在大多数EC反应和所有PEC反应中，只有电池的一个半反应被优化以产生价值;另一半反应牺牲了自己的电极或氧化还原添加剂。“成对”电解，其中两个半反应都提供有用的物种，是可持续性和效率的关键。HELIOS将发现，开发和推广成对的合成PEC反应。由两种半反应产生的中间体在新颖的、创造性的化学转化中会聚，包括：i）由每个半反应产生的自由基或离子的结合，以提供有价值的药物苯乙胺和氮杂环丁烷ii）提供双环支架的环融合反应，朝向药物发现中迫切需要的具有高3D特征的分子iii）催化的、环境友好的并且使用温和条件的醇转化反应将使用“多功能”催化剂，其可以在阴极和阳极半电池中被电活化，光化学产生和稳定活性中间体。HELIOS i）利用电能和光能快速转化廉价，丰富的化学原料转化为增值的复杂分子，以及ii）提高合成PEC和EC工艺的可持续性和选择性。HELIOS开辟了化学反应的全新维度，将彻底改变化学家使用氧化还原合成分子的方式。