Kolb, Simon
[VerfasserIn];
Brandt, Felix
[VerfasserIn];
Jacob, Christoph R.
[VerfasserIn];
Jones, Peter G.
[VerfasserIn];
Petzold, Martin
[VerfasserIn];
Werz, Daniel B.
[VerfasserIn]
Electrocatalytic Activation of Donor–Acceptor Cyclopropanes and Cyclobutanes
Beschreibung:
We describe the first electrochemical activation of D–A cyclopropanes and D–A cyclobutanes leading after C(sp3)−C(sp3) 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.