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Nef Reaction with Molecular Oxygen in the Absence of Metal Additives, and Mechanistic Insights

“… Molecular oxygen has previously been employed as an oxidant in the Nef reaction, but only when facilitated by metal catalysts 16. 17 There is one mechanism‐based study, as far as we were aware, that reports the conversion of potassium nitronate into the corresponding ketone in dimethyl sulfoxide (DMSO) in low yield (10 %) 25. Because the base‐promoted transformation of nitro compounds into carbonyl derivatives with molecular oxygen is rare, optimization of the reaction conditions under an O 2 atmosphere was performed (Table 1).…”

“…Oxidative methods are also known, and a nitro compound can be converted into a carbonyl derivative by oxidizing reagents such as KMnO 4 ,3 m ‐chloroperoxybenzoic acid (MCPBA),4 MoO 5 –pyridine–HMPA,5 ceric ammonium nitrate,6 hydrogen peroxide,7 ozone,8 singlet oxygen,9 t BuOOH/VO(acac) 2 ,10 Oxone,11 sodium chlorite,12 dimethyldioxirane,13 tetrapropylammonium perruthenate,14 or m ‐iodoxybenzoic acid 15. Molecular (triplet) oxygen has been used as an oxidant, but these typically necessitate the use of metal catalysts such as [Cu(tmeda)(NO 2 ) 2 ]16 and [Fe(Hdmg) 2 (py) 2 ] 17. The Nef reaction can also be carried out with reducing reagents such as aqueous titanium trichloride,18 vanadium chloride,19 and chromium chloride 20.…”

Kinetics and mechanism of the oxygenation of potassium nitronates. Evidence for a single electron transfer (SET) mechanism

“…Since this is an ironcontaining enzyme we initiated studies on copper-and iron-mediated oxygenations of nitroalkanes. We could show that isopropyl nitronate, ligated to copper or iron ions, can be oxygenated to (nitrito)metal species and acetone, and in the presence of copper metal, as a precursor, nitroalkanes are easily transformed to aldehydes or ketones by dioxygen [18][19][20][21]. Nitroalkaneoxidizing enzyme from the extract of Neurospora crassa oxidatively metabolizes nitroalkane and showed that it is a 2-nitropropane dioxygenase too [17].…”

Catalytic oxidation of alcohols to carbonyl compounds with hydrogen peroxide using dinuclear iron complexes

“…While oxidation of alcohols was accomplished by H 2 O 2 utilizing catalytic amounts of Fe(III) salts [14,15], so far little effort has been devoted to the use of non-heme iron complexes as catalysts. The complex [Fe(Hdmg) 2 (py) 2 ] was found to be selective catalyst for the oxidative denitrification of nitroalkanes [16]. Feringa and coworkers [17] [18], and [Fe 2 (OMe) 2 (PAP)Cl 4 ] (2) (PAP = 1,4-di(2 -pyridyl)aminophthalazine) [19] in order to modeling soluble methane monooxygenase (sMMO).…”