AcrH₂ As The Photocatalyst Catalyzed Arylation Of （Hetero）Arenes With Aryl Diazonium Salts And The CuI-Catalyzed α-Acyloxylation Of Acetone With Carboxylic Acids

The NADH coenzyme model compounds’ environmental friendliness and wide availability that can, in some case, outperform the inorganic and organometallic counterparts, have been recognized and extensively investigated for applications. And particular, reducing α,β-unsaturated ketones, activated olefins, and α,β-epoxy ketones and oxidizing sulfides, which catalyzed by the NADH coenzyme model compounds, have already known to us. Despite their wide employment, these transformations are almost exclusively leading to self reduction and oxygenation. Arylated heteroarenes represent an attractive building block in the synthesis of natural products, pharmaceuticals, and materials. Over the past decades, the transition-metal or nonmetal catalyzed directed C-H arylation have been wildly used for the construction of arylated heteroarenes. Recently, the visible light photoredox catalysis, relying on the ability of phototcatalysts to engage in single-electron-transfer (SET) processes with organic substrates, has emerged as a powerful platform for the development of new reactions in organic synthesis. We repored AcrH2-catalyzed direct C-H arylation of (hetero)arenes coupling with aryl diaznium salts under visible light irradiation was reported for the first time.a-acyloxylation of carbonyl compounds represent attractive building blocks in the synthesis of natural products, pharmaceuticals, and biologically active molecules and have broad utility as significant synthetic intermediates. Over the past few years, the synthesis of these a-acyloxycarbonyl compounds were through the substitution of a-halocarbonyl compounds wth carboxylates or catalyzed addition of carboxylic acids onto propargyl alcohols. However, these coupling reactions required functionalized reactants, prefunctionalization of ketones/carboxylic acids, which decreases the atom economy. Recently, direct oxidative coupling of ketones with carboxylic acids using a hypervalent iodine catalyst has been reported to give the α-acyloxyketones. However, in spite of these great developments in the synthesis of a-oxyacylation of carbonyl compounds, there is still limited success in direct acyloxylation with the methyl of a-carbonyl. Herein, we first reported a CuI as the iodine reagent catalyzed cross-dehydrogenative coupling with the methyl of acetone to form a-acyloxylation of carbonyl compounds.