Photoinduced Copper(I)‐Catalyzed Cyanation of Aromatic Halides at Room Temperature

Abstract

Thef irst photoinduced copper(I)-catalyzed cyanation of aromatich alides at room temperature hasb een developed. The sp 2 cyanation reaction exhibitso utstanding tolerance to functional groups including primary amines and carboxylic acids,a nd chemoselectivity to S N 2-reactive alkyl chlorides.M echanistic investigationsi ndicate that the reactiono ccurs via as ingle-electron transfer (SET) between the aryl halide and an excited copper(I) cyanide catalytic intermediate.

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

“…Mechanistic investigations show that the aforementioned catalytic reaction proceeded by single electron transfer (SET) between the aryl halide and an excited copper(I) cyanide in the intermediate steps of the catalytic reaction (See Figure 1). [9] …”

A photoresponsive palladium complex of an azopyridyl-triazole ligand: light-controlled solubility drives catalytic activity in the Suzuki coupling reaction

“…Such photoinduced dehalogenations are precedented in the literature and likely proceed via the formation of an aryl radical that abstracts one hydrogen from the solvent. [31][32][33] Due to the larger conversions in response to increased light intensity along with decreased selectivity toward the production of the coupled product, we explored how shorter irradiation times would affect the conversion and the product ratio. For this, aer the addition of the cis-rich 5-Pd solution, the reaction mixture was irradiated for 30 min (30 W), and then the light was switched off for the rest of the reaction time.…”

Light-emitting diode light–enabled denitrative etherification of 4-nitrobenzonitrile under catalyst-free conditions at room temperature

“…The solvent was evaporated leaving the crude product, which was purified by column chromatography over silica gel using n-hexane/ethylacetate (8:2) as the eluent. 4-Ethoxybenzonitrile (3a): 24 Yellow solid; 1H NMR (300 MHz, CDCl 3 ) δ; 1.48 (t, J = 7.0 Hz, 3 H), 4.11 (q, J = 7.0 Hz, 2 H), 6.96 (dd, J = 7.0 Hz, J ʹ = 1.9 Hz, 2 H), 7.61 (dd, J = 6.9 Hz, J ʹ = 2.0 Hz, 2 H); 13C NMR (75 MHz, CDCl…”