Quinone-mediated hydrogen anode for non-aqueous reductive electrosynthesis-猫眼课题宝

DOI：

10.1038/s41586-023-06534-2

发表时间：

2023-08

期刊：

Nature

影响因子：

64.8

通讯作者：

中科院分区：

综合性期刊1区

文献类型：

作者：

Jack Twilton;Mathew R. Johnson;Vinayak Sidana;Mareena C. Franke;C. Bottecchia;Dan Lehnherr;F. Lévesque;S. M. Knapp;Luning Wang;James B. Gerken;Cynthia M. Hong;T. Vickery;M. D. Weisel;N. Strotman;D. Weix;T. Root;S. Stahl

电化学合成可以为工业化学品提供更可持续的途径，-。电合成氧化通常可以“无试剂”进行，产生来自底物的氢气 (H2)，作为对电极的唯一副产品。然而，电合成还原需要外部电子源。牺牲金属阳极通常用于小规模应用，但大规模应用需要更可持续的选择。阳极水氧化是一种特别有吸引力的选择，但许多还原需要无水、无空气的反应条件。在这种情况下，H2 是一种理想的替代品，激发了人们对非水条件下电化学氢氧化反应 (HOR) 的兴趣日益浓厚，,,,,–。在这里，我们报道了一种介导的 H2 阳极，通过将蒽醌介体的热催化氢化与蒽氢醌的电化学氧化配对来实现 H2 的间接电化学氧化。这种醌介导的 H2 阳极用于支持镍催化的交叉亲电子偶联 (XEC)，这是一种在制药行业得到广泛采用的反应类别。在小规模批量反应中对该方法进行了初步验证，然后适应循环流反应器，从而能够实现百克规模的药物中间体合成。这里公开的介导的H 2 阳极技术提供了支持H 2 驱动的电合成还原的一般策略。

Electrochemical synthesis can provide more sustainable routes to industrial chemicals, –. Electrosynthetic oxidations may often be performed ‘reagent-free’, generating hydrogen (H2) derived from the substrate as the sole by-product at the counter electrode. Electrosynthetic reductions, however, require an external source of electrons. Sacrificial metal anodes are commonly used for small-scale applications, but more sustainable options are needed at larger scale. Anodic water oxidation is an especially appealing option,,, but many reductions require anhydrous, air-free reaction conditions. In such cases, H2represents an ideal alternative, motivating the growing interest in the electrochemical hydrogen oxidation reaction (HOR) under non-aqueous conditions, , , , –. Here we report a mediated H2anode that achieves indirect electrochemical oxidation of H2by pairing thermal catalytic hydrogenation of an anthraquinone mediator with electrochemical oxidation of the anthrahydroquinone. This quinone-mediated H2anode is used to support nickel-catalysed cross-electrophile coupling (XEC), a reaction class gaining widespread adoption in the pharmaceutical industry, –. Initial validation of this method in small-scale batch reactions is followed by adaptation to a recirculating flow reactor that enables hectogram-scale synthesis of a pharmaceutical intermediate. The mediated H2anode technology disclosed here offers a general strategy to support H2-driven electrosynthetic reductions.

Quinone-mediated hydrogen anode for non-aqueous reductive electrosynthesis

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