Affiliation:
1. State Key Laboratory of Applied Organic Chemistry College of Chemistry and Chemical Engineering Lanzhou University Lanzhou 730000 China
2. CAS Key Laboratory of Photochemistry Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China
3. Key Laboratory of Photochemical Conversion and Optoelectronic Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing 100190 P. R. China
Abstract
AbstractDearomative spirocyclization reactions represent a promising means to convert arenes into three‐dimensional architectures; however, controlling the regioselectivity of radical dearomatization with nonactivated arenes to afford the spirocyclizative 1,2‐difunctionalization other than its kinetically preferred 1,4‐difunctionalization is exceptionally challenging. Here we disclose a novel strategy for dearomative 1,2‐ or 1,4‐amidoximation of (hetero)arenes enabled by direct visible‐light‐induced homolysis of N−NO bonds of nitrosamides, giving rise to various highly regioselective amidoximated spirocycles that previously have been inaccessible or required elaborate synthetic efforts. The mechanism and origins of the observed regioselectivities were investigated by control experiments and density functional theory calculations.
Funder
National Natural Science Foundation of China