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Electrocatalytic Activation of Donor–Acceptor Cyclopropanes and Cyclobutanes: An Alternative C(sp 3 )−C(sp 3 ) Cleavage Mode
Author(s) -
Kolb Simon,
Petzold Martin,
Brandt Felix,
Jones Peter G.,
Jacob Christoph R.,
Werz Daniel B.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202101477
Subject(s) - cyclobutanes , chemistry , electrochemistry , cleavage (geology) , photochemistry , reaction mechanism , acceptor , bond cleavage , stereochemistry , medicinal chemistry , catalysis , organic chemistry , cycloaddition , electrode , physics , geotechnical engineering , fracture (geology) , engineering , condensed matter physics
We describe the first electrochemical activation of D–A cyclopropanes and D–A cyclobutanes leading after C(sp 3 )−C(sp 3 ) cleavage to the formation of highly reactive radical cations. This concept is utilized to formally insert molecular oxygen after direct or DDQ‐assisted anodic oxidation of the strained carbocycles, delivering β‐ and γ‐hydroxy ketones and 1,2‐dioxanes electrocatalytically. Furthermore, insights into the mechanism of the oxidative process, obtained experimentally and by additional quantum‐chemical calculations are presented. The synthetic potential of the reaction products is demonstrated by diverse derivatizations.