Direct Synthesis of 1,2-Diketones by Catalytic Aerobic Oxidative Decarboxylation of 1,3-Diketones with Iodine and Base under Irradiation of Fluorescent Light

Abstract

We report a catalytic direct synthesis of 1,2-diketone from 1,3-diketone through iodine/base-catalyzed aerobic photooxidation under visible-light irradiation of fluorescent lamp.

Light-induced O2-dependent aliphatic carbon–carbon (C–C) bond cleavage in bipyridine-ligated Co(ii) chlorodiketonate complexes

“…6b Under dry conditions, benzoic anhydride is formed and quantitative 18 O incorporation is found in a 1,3diphenylpropanetrione intermediate. We note that a bipyridine-ligated Cu(II) chlorodiketonate complex, [(bpy)Cu(PhC(O) C(Cl)C(O)Ph)]ClO 4 (7), is also reactive with O 2 under ambient conditions. 6c Notably, use of the tetradentate tris(2-pyridylmethyl)amine supporting ligand in a Cu(II) chlorodiketonate complex results in a non-redox, water-dependent retro-Claisen pathway becoming more prevalent for aliphatic C-C cleavage.…”

“…In support of this proposal, α-I-β-diketones have been reported to undergo reaction with O 2 under illumination to produce 1,3-diphenylpropanetrione, PhC(O)C(O)C(O)Ph. 7 Notably, analogs of 1 having p-methyl or p-H chlorodiketonate ligands exhibit significantly lower levels of oxidative C-C bond cleavage reactivity, indicating that the electronic structure of the diketonate ligand has an impact on the photoinduced reactivity in this system. 6a A Cu(II) chlorodiketonate complex supported by the same 6-Ph 2 TPA ligand (5, Scheme 1(b)) exhibits thermal O 2 -mediated C-C bond cleavage reactivity in the presence of added chloride anion at room temperature.…”

Iodine and DMSO as Surrogate of Hazardous Metal and Non‐Metal Reagents in Organic Synthesis

“…Apart from the numerous methods of preparation of 1,2‐dicarbonyl esters, there are some discuss worthy protocols leading to the formation of aforementioned moieties. Several methods have been reported for the synthesis of 1,3‐diketone derivatives, including those using metal catalysts supported by oxidants and those using inorganic bases such as calcium hydroxide in combination with catalytic molecular iodine system (Scheme 65 (a–d)) [662–665] . In 2020, Malakar and his team successfully synthesized the target molecule by using derivatives of diphenyl acetylene and HFIP (Scheme 65 (e)) [666] .…”

Transition metal-free, photocatalytic arylation and dioxygenation for vicinal diketone synthesis using alkynes and arene diazonium salts

“…5,6 As one of the main targets of difunctionalization of multiple carbon–carbon bonds, vicinal diketones are important precursors for numerous biologically functional molecules and are broadly utilized for the construction of complex structures in organic synthesis. 7 As outlined in Scheme 1, an array of methods for the preparation of vicinal diketones are currently known by means of direct oxidation on single substrates such as stilbenes (Scheme 1A), 8 1,3-diketones (Scheme 1B), 9 alkynones (Scheme 1C), 10 internal alkynes (Scheme 1D) 11 and some other precursors. 12 Alongside the direct oxygenation on one precursor, the reactions involving oxygenation and coupling of two different components have also been proved to be applicable for vicinal diketone synthesis.…”