Electrocatalytic Activation of Donor-Acceptor Cyclopropanes and Cyclobutanes: An Alternative C(sp3)-C(sp3) Cleavage Mode.

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 ꞵ- 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 po-te-n-tial of the reaction products is demonstrated by diverse derivatizations .