Binuclear copper iodine cluster-based coordination sheets as photocatalysts for decarboxylative cyanation

Abstract

We synthesized two new MOFs (Cu-Tpxa-1 and Cu-Tpxa-2) that were used as heterogeneous photocatalysts, combining photocatalysis and copper catalysis to achieve the decarboxylative radical cyanation reactions. The new heterogeneous catalysis...

Photoelectroactive metal–organic frameworks

“…245 Copyright 2020, Elsevier. cycloaddition, 77 decarboxylative radical cyanation, 266 and debromination. 267 For instance, a Cr MOF photocatalyst Cr-PCN-600 that was constructed from Cr(NO 3 ) 3 $9H 2 O and H 2 TCPP was reported to oxidize benzyl alcohol to benzaldehyde, which exhibited a conversion of 98% and selectivity above 99% in the presence of O 2 (1 atm) at 32 °C (±3) under visible light LED irradiation (Scheme 8a).…”

“…Organic syntheses with selectivity for oxidation/reduction/cycloaddition reactions using photocatalysts are appealing. 46,248,249 These photocatalytic organic transformations include but are not limited to the oxidation of alcohols, 250,251 oxidation of amines, 75,252–256 oxidation of sulfides, 76,257–260 reduction of nitroarenes, 261–263 C–C/C–N/C–halogen couplings, 78,251,256,259,264,265 cycloaddition, 77 decarboxylative radical cyanation, 266 and debromination. 267…”

Copper-Catalyzed Enantioselective Decarboxylative Cyanation of Benzylic Acids Promoted by Hypervalent Iodine(III) Reagents

“…To our delight, with a catalytic system comprising CuF 2 (10 mol %), chiral bisoxazoline ligand L1 (15 mol %), hypervalent iodine(III) reagent (PhIO, 2.0 equiv), and K 2 HPO 4 ·3H 2 O (1.5 equiv), the decarboxylative cyanation reaction proceeded smoothly in acetone at 30 °C, affording the desired cyanide product 2a in 66% yield with 96:4 er (entry 1). The absolute configuration of product 2a was assigned to be R by comparison with the reported data. , Then, a variety of Cu(II) and Cu(I) catalysts were investigated, and Cu(acac) 2 exhibited the best reactivity to provide 2a in 85% yield with 96:4 er (entries 2–4). Notably, this transformation was found to be highly sensitive to the ligand.…”

“…Based on the above mechanistic experiments and existing related literature, ,− , a plausible reaction mechanism was proposed (Scheme ). The carboxylic acid 1 would first be activated in situ by ligand exchange with PhIO, forming phenyliodine(III) dicarboxylates 6 with the assistance of base.…”

Concave octopus-like PtCu nanoframe mediated photo-electro Fenton catalysis for fast organic dyestuff elimination

“… 19 Compared to conventional Fenton treatments, photo-electro Fenton processes exhibit better reactive environmental adaptability due to the self H 2 O 2 -production profile. 20 With the treatment of direct current (DC), gaseous oxygen (O 2 ) is transferred into the solution in the cathode region and continuously decomposes into two oxygen atoms for the electrochemical oxidation of H 2 O 2 . Whereafter, the resultant H 2 O 2 can react with Fenton agents (ferrous, manganese and copper ions, customarily) to homogeneously generate superoxidized ˙OH, 21 and thus chemically oxidize the organic dyestuff pollutants to CO 2 , H 2 O and inorganic salts, ultimately.…”