Oxone® Promoted Nef Reaction. Simple Conversion of Nitro Group Into Carbonyl

Total synthesis of natural products containing benzofuran rings

“…246 A new and efficient method for the synthesis of linear furocoumarins was reported by the Nef reaction. 247 This strategy has also been applied to the preparation of four additional benzofuran derivatives. A mixture of 2,4-dihydroxybenzaldehyde and nitromethane was stirred in AcOH in the presence of NH 4 OAc to give 5-hydroxy-2-(2-nitroethenyl) phenol 236 (ref.…”

Synthesis of Some 2-Aminonitroethanes via Silica Gel-Catalyzed Nitro-Mannich Reaction

“…Functionalities present in the products may be suitable for a wide range of other chemical manipulations. The CH 2 NO 2 unit, for example, can be transformed into a carbonyl group by the Nef reaction [5], and then to carboxylic acid, making products 3 precursors to some α-amino acids. The feasibility of replacing the nitro group by hydrogen atom (denitration) using tributyltin hydride is also important [6].…”

Sulfur and Phosphorus Peroxides

“…Under these conditions 5-nitrohexan-2-ol does not react, probably as a consequence of an intramolecular hydrogen shift from the hydroxyl group to the nitronate carbanion, in a six-membered transition state which prevents the oxidation of the nitro derivative. When the hydroxyl group is protected by an acyl or a tertbutyldimethylsilyl (TBDMS) group, the nitro group is oxidized to a carbonyl group in good yield (equation 68) 194 Oxone is a cheap oxidant but contains only about 50% of active oxidant per mol of the triple salt. Some methods 196 have been developed to prepare the pure potassium monoperoxysulfate (KHSO 5 ), yet this purified oxidant have not been tried in organic synthesis, perhaps due to less convenient procedures for obtaining the pure oxidant.…”