An Effective General Method for Oxidizing Salts of Mononitro Compounds with Neutral Permanganate to Aldehydes and Ketones^1a

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

“…The classical Nef reaction is carried out under acidic conditions using strong acid such as aqueous HCl 2. 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.…”

Palladium-Catalyzed Nitromethylation of Aryl Halides: An Orthogonal Formylation Equivalent

“…23 Indeed, exhaustive attempts at utilizing hydrolytic Nef conditions failed on these substrates, providing only recovered substrate. Use of commonly employed KMnO 4 yielded significant amounts of oxidatively coupled dimers, 24 even when conducted under extremely dilute conditions. We discovered that a modified procedure using tin(II) chloride 25 was most effective and permitted a far wider range of functional groups to be employed (Table 3).…”

New synthesis of formaldehyde-d2

“…When this reaction, or the modification introduced by Schechter and Williams (12) was applied to nitromethane, little if any formaldehyde was produced. Since this reaction would have led to an aqueous solution of formaldehyde-d, containing large amounts of inorganic salts, it was not investigated further.…”