Ferroxime(II)-catalyzed oxygenation of nitroalkanes by tert-butyl hydroperoxide and its relevance to 2-nitropropane dioxygenase

Kaizer, József; Gréczi, Zoltán; Speier, Gábor

doi:10.1016/s1381-1169(01)00329-6

Cited by 6 publications

(2 citation statements)

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“…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).…”

Section: Resultsmentioning

confidence: 99%

“…[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] NaOMe/silica gel is also effective for this conversion.…”

Section: Introductionmentioning

confidence: 99%

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

Umemiya

Nishino

Sato

et al. 2014

Chemistry A European J

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A Nef reaction has been developed that is conducted under mildly basic conditions with molecular oxygen as an oxidant, without the need for metal additives. Whereas nitroalkanes are converted into ketones in good yield, nitroalkenes are transformed into α,β-unsaturated ketones in one-pot by double-bond isomerization followed by the oxygen-mediated Nef reaction. The reaction protocol is both mild and general, and tolerates acid- and base-labile functionality or protecting groups. When oxygen-saturated solvents are employed, the reaction completes within 20 min. Mechanistically, the addition of nitronate ion and molecular oxygen is proposed to proceed initially through a single-electron transfer event, as indicated by radical clock experiments. This ultimately generates a putative 1,1-dioxirane, which reacts further with another nitronate ion to generate the ketone. Involvement of a 1,1-dioxirane is supported by intramolecular trapping experiments with sulfide at the γ-position of the nitro-moiety.

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Section: Resultsmentioning

confidence: 99%