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Electrocatalytic hydrogenation of quinolines with water over a fluorine-modified cobalt catalyst
Nature Communications ( IF 14.7 ) Pub Date : 2022-09-08 , DOI: 10.1038/s41467-022-32933-6
Shuoshuo Guo 1 , Yongmeng Wu 1 , Changhong Wang 1 , Ying Gao 1 , Mengyang Li 1, 2 , Bin Zhang 1, 3 , Cuibo Liu 1, 3
Affiliation  

Room temperature and selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines using a safe and clean hydrogen donor catalyzed by cost-effective materials is significant yet challenging because of the difficult activation of quinolines and H2. Here, a fluorine-modified cobalt catalyst is synthesized via electroreduction of a Co(OH)F precursor that exhibits high activity for electrocatalytic hydrogenation of quinolines by using H2O as the hydrogen source to produce 1,2,3,4-tetrahydroquinolines with up to 99% selectivity and 94% isolated yield under ambient conditions. Fluorine surface-sites are shown to enhance the adsorption of quinolines and promote water activation to produce active atomic hydrogen (H*) by forming F-K+(H2O)7 networks. A 1,4/2,3-addition pathway involving H* is proposed through combining experimental and theoretical results. Wide substrate scopes, scalable synthesis of bioactive precursors, facile preparation of deuterated analogues, and the paired synthesis of 1,2,3,4-tetrahydroquinoline and industrially important adiponitrile at a low voltage highlight the promising applications of this methodology.



中文翻译:

氟改性钴催化剂上喹啉与水的电催化加氢

由于喹啉和 H 2的活化困难,使用安全和清洁的氢供体在室温下选择性氢化喹啉为 1,2,3,4-四氢喹啉具有重要意义,但具有挑战性。在这里,通过电还原 Co(OH)F 前驱体合成了一种氟改性钴催化剂,该前驱体对喹啉的电催化加氢具有高活性,以 H 2 O 为氢源生成 1,2,3,4-四氢喹啉在环境条件下,选择性高达 99%,分离产率高达 94%。氟表面位点通过形成 F - -K +来增强喹啉的吸附并促进水活化以产生活性原子氢 (H*)(H 2 O) 7 个网络。通过结合实验和理论结果,提出了一种涉及H*的1,4/2,3-加成途径。广泛的底物范围、生物活性前体的可扩展合成、氘代类似物的简便制备以及低电压下 1,2,3,4-四氢喹啉和工业上重要的己二腈的配对合成突出了该方法的有前景的应用。

更新日期:2022-09-09
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