RESUMO
Photoredox catalysis has become an essential tool in organic synthesis because it enables new routes to important molecules. However, the best available molecular catalysts suffer from high catalyst loadings and rely on precious metals. Here we show that colloidal nanocrystal quantum dots (QDs) can serve as efficient and robust, precious-metal free, photoassisted redox catalysts. A single-sized CdSe quantum dot (3.0 ± 0.2 nm) can replace several different dye catalysts needed for five different photoredox reactions (ß-alkylation, ß-aminoalkylation, dehalogenation, amine arylation, and decarboxylative radical formation). Even without optimization of the QDs or the reaction conditions, efficiencies rivaling those of the best available metal dyes were obtained.
RESUMO
A new method for the decarboxylative coupling of alkyl N-hydroxyphthalimide esters (NHP esters) with aryl iodides is presented. In contrast to previous studies that form alkyl radicals from carboxylic acid derivatives, no photocatalyst, light, or arylmetal reagent is needed, only nickel and a reducing agent (Zn). Methyl, primary, and secondary alkyl groups can all be coupled in good yield (77% ave yield). One coupling with an acid chloride is also presented. Stoichiometric reactions of (dtbbpy)Ni(2-tolyl)I with an NHP ester show for the first time that arylnickel(II) complexes can directly react with NHP esters to form alkylated arenes.
