Kolb Simon, Petzold Martin, Brandt Felix, Jones Peter G, Jacob Christoph R, Werz Daniel B
Technische Universität Braunschweig, Institute of Organic Chemistry, Hagenring 30, 38106, Braunschweig, Germany.
Technische Universität Braunschweig, Institute of Physical and Theoretical Chemistry, Gaußstraße 17, 38106, Braunschweig, Germany.
Angew Chem Int Ed Engl. 2021 Jul 12;60(29):15928-15934. doi: 10.1002/anie.202101477. Epub 2021 Jun 16.
We describe the first electrochemical activation of D-A cyclopropanes and D-A cyclobutanes leading after C(sp )-C(sp ) 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.
我们描述了首例D-A环丙烷和D-A环丁烷的电化学活化反应，该反应在C(sp³)-C(sp³)键断裂后生成高活性自由基阳离子。通过直接或DDQ辅助的阳极氧化，将这一概念应用于张力碳环，从而在电催化作用下引入分子氧，生成β-和γ-羟基酮以及1,2-二氧六环。此外，还介绍了通过实验和额外的量子化学计算获得的关于氧化过程机理的见解。通过多种衍生化反应展示了反应产物的合成潜力。
