Selective electrochemical acceptorless dehydrogenation reactions of tetrahydroisoquinoline derivatives

Selective dehydrogenation reactions of tetrahydroisoquinoline derivatives through electrochemical oxidation are disclosed. In the presence of nitric acid, the selective partial dehydrogenation of tetrahydroisoquinolines to form 3,4-dihydroisoquinolines was achieved via anodic oxidation. The results...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2024-01, Vol.22 (4), p.725-73
Main Authors: Li, Pan, Tian, Yue, Tian, Lifang, Wang, Yahui
Format: Article
Language:English
Subjects:
Anodizing
Chemical reactions
Dehydrogenation
Electrochemical oxidation
Electrochemistry
Nitric acid
Oxidation
Tetrahydroisoquinoline
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Summary:Selective dehydrogenation reactions of tetrahydroisoquinoline derivatives through electrochemical oxidation are disclosed. In the presence of nitric acid, the selective partial dehydrogenation of tetrahydroisoquinolines to form 3,4-dihydroisoquinolines was achieved via anodic oxidation. The results of CV (Cyclic Voltammograms) experiments and DFT calculations showed the 3,4-dihydroisoquinolines protonated by an external Brønsted acid to be less prone than their unprotonated counterparts to oxidation under electrochemical conditions, thus avoiding their further dehydrogenation. Moreover, a TEMPO-mediated electrochemical oxidation enabled a complete dehydrogenation to yield fully aromatized isoquinolines. Thus, tunable processes involving electrochemical dehydrogenation of tetrahydroisoquinolines could be used to selectively produce various 3,4-dihydroisoquinolines and isoquinoline derivatives. The selective formation of 3,4-dihydroisoquinolines was achieved by incapacitating their further oxidation through an in situ protonation with an external Brønsted acid.
ISSN:1477-0520
1477-0539
DOI:10.1039/d3ob01930f