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; 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.

可见光和电能的协同作用已在水分裂为氢中已有数十年，但直到最近才用于供应较高价值的复杂有机分子（天然产物，药物）的合成。合成光电化学（PEC）与单独的光学或电化学相比，其氧化还原转化，可持续性和选择性的增强范围，引起了人们的关注。合成电化学（EC）是一种有用的合成工具，可以用简单的电子和质子代替原子不经济的化学氧化还原剂。但是，在大多数EC反应和所有PEC反应中，仅对细胞的一半反应进行了优化以产生值。其他半反应牺牲了自己的电极或氧化还原添加剂。两种半反应提供有用物种的“配对”电解是可持续性和效率的关键。Helios将发现，发展和传播配对的合成PEC反应。两种半反应产生的中间体都在新颖的创意化学转化中融合，包括：i）每种半反应产生的激进物或离子结婚，以提供苯乙胺和偶氮胺的提供，值得的药物 - 拟态拟曲，从而带有与3D特性的分子相关的反应，从而提供了与3D特性的反应相关的反应将使用催化性，对环境友好并使用轻度条件的催化剂，可以在阴极和阳极的半元素中进行电激活，以光化学产生和稳定反应性中间体。合成PEC和EC过程。 Helios打开了一个全新的化学反应性维度，这将彻底改变化学家使用氧化还原来合成分子的方式。