RESUMO
Aryl amination is an essential transformation for medicinal, process, and materials chemistry. In addition to classic Buchwald-Hartwig amination conditions, blue-light-driven metallaphotoredox catalysis has emerged as a valuable tool for C-N cross-coupling. However, blue light suffers from low penetration through reaction media, limiting its scalability for industrial purposes. In addition, blue light enhances unwanted side-product formation in metallaphotoredox catalysis, namely hydrodehalogenation. Low-energy light, such as deep red (DR) or near-infrared (NIR), offers a solution to this problem as it can provide enhanced penetration through reaction media as compared to higher-energy wavelengths. Herein, we show that low-energy light can also enhance the desired reactivity in metallaphotoredox catalysis by suppressing unwanted hydrodehalogenation. We hypothesize that the reduced side product is formed by direct photolysis of the aryl-nickel bond by the high-energy light, leading to the generation of aryl radicals. Using deep-red or near-infrared light and an osmium photocatalyst, we demonstrate an enhanced scope of (hetero)aryl bromides and amine-based nucleophiles with minimal formation of hydrodehalogenation byproducts.
Assuntos
Luz , Níquel , Catálise , Aminação , Níquel/química , Brometos/químicaRESUMO
The non-innocence of diamidodipyrrin is explored in a series of cobaltous complexes with novel binding motifs. By varying the coordination modes, a reversible one-electron reduction is remarkably shifted by nearly 200 mV in a single metal-ligand platform. Our study illustrates a new strategy for modifying the redox activity of porphyrin-like scaffolds.
