A Novel Construction of Dibenzofuran-1,4-diones by Oxidative Cyclization of Quinone-arenols

Abstract

A novel oxidative cyclization of quinone-arenols 5 leading to products 6 with a dibenzofuran-1,4-dione structure, which forms the core of several natural products, has been developed and applied to the synthesis of violet-quinone (4).

The biomimetic synthesis of balsaminone A and ellagic acid via oxidative dimerization

“…Biomimetic synthesis of balsaminone A With the initial focus being the biomimetic synthesis of balsaminone A (4), well-established methods for the dimerization of phenolic compounds were explored [8,9]. As such, a methanolic solution of 2-methoxy-1,4-dihydroxynaphthalene (8), obtained from the reduction of lawsone (6), was subjected to the oxidants activated carbon (Act-C), potassium ferricyanide (K 3 [Fe(CN) 6 ]), p-benzoquinone and stannic chloride (SnCl 4 ). As shown in Scheme 4, with the exception of SnCl 4 , all oxidants resulted in the re-oxidation of the hydroxylated substrate to naphthoquinone 7.…”

“…Alternatively, the binaphthylquinone 16 was synthesized through the oxidation of lawsone ( 6 ), in the presence of sodium persulfate, followed by methylation [ 25 ]. The cyclization of binaphthyl 16 was then attempted taking into consideration the photolytic cyclization of binaphthyls to form pentacyclic furan derivatives [ 8 , 18 , 22 ]. However, the photolytic cyclization of binaphthyl 16 using a 100 W bulb was attempted without success, due to degradation of the starting material.…”

“…Throughout the years, the exploration of oxidative dimerization reactions of electron-rich aromatic compounds, such as thiophenes, anilines and alkoxyarenes, in an attempt to establish high-yielding and selective oxidative coupling reactions, has afforded new and greener synthetic protocols for biaryls [ 5 – 7 ]. Several oxidants, such as the salts of Ag(I&II) [ 8 ], Ti(III&IV) [ 9 ], Mn(III) [ 10 ], Ce(IV) [ 11 ], Sn(IV) [ 12 ] and Fe(III) [ 13 ], as well as the hypervalent iodine reagents phenyliodine diacetate (PIDA) and phenyliodine bis(trifluoroacetate) (PIFA), have been utilized for oxidative dimerization reactions [ 14 – 15 ]. The use of these one-electron oxidants, as well as non-metallic reagents, plays an important role in accessing symmetrical and asymmetrical biaryls and polyaryls [ 1 ].…”

The Synthesis, Characterization, and Electrochemical Investigation of Novel Thio- and Alkoxy-Substituted Benzoquinone Derivatives

“…[1][2][3][4][5][6] Heterocyclic ring quinone systems are found in biologically and pharmacologically active compounds. 7 It is also known from the literature that substitution of quinonoid structure with N-, S-, and O-nucleophiles leads to an observable increase in biological activity. 8 Many natural products from marine or plant sources involve quinonoid structures with important biological activity properties.…”

Synthesis of benzonaphthofuroquinones and benzoylnaphthindolizinediones by reactions of flavonoids with dichlone under basylous, oxygenous and aqueous conditions: their cytotoxic and apoptotic activities

“…9 Quinone-arenols were prepared from hydroquinone monomethylethers by oxidants to form C-C bond in the rst step, and by oxidative cyclization of quinone-arenols to give C-O bond in the second step to produce dibenzofuranquinones. 10 In reported methods, benzoylnaphthindolizinediones (adunnione-like compounds) were synthesized by potassium carbonate-catalyzed one-pot tandem reactions of the N-ylides with 2,3-dichloro-1,4-naphthoquinone (Scheme 3, (1)), 11 or by copper(II)-catalyzed three-component reactions of 2-bromoacetophenone, 1,4-naphthoquinone, and pyridine via sp 2 -C-H difunctionalization of naphthoquinone followed by intramolecular cyclization and oxidative aromatization (Scheme 3, (2)), 12 or by iodine oxidation of 2-alkyl-1,4-naphthoquinones in the presence of substituted pyridines (Scheme 3, (3)). 13 In our initial plan, in order to get naphthanaphthofuroquinones, dihydroavone and chalcone were respectively used to react with dichlone in pyridine under anoxic and anhydrous conditions, however, no targeted products were obtained.…”