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

几十年来，可见光和电能的协同作用一直被用于水分解成氢，但直到最近才被用于合成更高价值的复杂有机分子（天然产物，药物）。与光化学或电化学相比，合成光电化学（PEC）由于其氧化还原转化的范围、可持续性和选择性的增强而受到广泛关注。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代替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，只有一个半反应的细胞被优化产生值；另一半反应牺牲了自己的电极或氧化还原添加剂。“配对”电解，其中两个半反应提供有用的物质，是可持续性和效率的关键。HELIOS将发现、发展和传播成对的合成PEC反应。由两个半反应产生的中间体在新的、创造性的化学转化中融合，包括：i)由每个半反应产生的自由基或离子结合，以提供苯乙胺和氮杂啶，这是有价值的药物；i)提供双环支架的环融合反应，向药物发现迫切需要的具有高3D特性的分子提供；iii)催化的醇转化反应。“多功能”催化剂将在阴极和阳极半电池中被电激活，用于光化学生成和稳定反应中间体。HELIOS 1)利用电能和光能迅速将廉价、丰富的化学原料转化为增值的复杂分子，2)提高合成PEC和EC过程的可持续性和选择性。HELIOS开启了化学反应的一个全新维度，将彻底改变化学家使用氧化还原合成分子的方式。

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.