Substitution reactions which proceed via radical anion intermediates. 21. Rearrangements in the reaction of .beta.-arylated nitroparaffins with the sodium salt of methanethiol

Abstract

Rearrangements occur when /3-arylated nitroparaffins react with the sodium salt of methanethiol, a finding which provides support for the view that these reactions involve a spiro free radical intermediate.1 By invoking spiro free radicals one can explain the striking solvent and substituent effects observed in the reactions of nitroparaffins with the sodium salt of methanethiol. A minor side reaction-fragmentation of radical anions derived from /3-arylated nitroparaffins-is described.

Rapid syntheses of protected 2'-deoxycytidine derivatives

“…2,3,4,5,6-Pentafluorophenol (2.9 g, 15.7 mmol) was dissolved in dry dimethylformamide and stirred, protected from moisture, at 0-5 °C. Benzoic acid (1.92 g, 15.7 mmol) was then added, followed by redistilled dicyclohexylcarbodiimide (3.5 g, 16.9 mmol). After being stirred for 1 h, the mixture was filtered and the solvent evaporated as described.…”

The Last Fortress of Tin's Tyranny – Protodenitration of Nitroalkanes

“…In follow-up papers in 1979, Kornblum expanded the scope of the methodology and proposed a plausible mechanism. [27,28] According to his findings, the reduction proceeds via an anionfree radical chain mechanism (Scheme 4). Although the sodium thiomethoxide-mediated reduction provided excellent chemical yields, it has not found many applications in targeted synthesis.…”

“…In follow‐up papers in 1979, Kornblum expanded the scope of the methodology and proposed a plausible mechanism [27,28] . According to his findings, the reduction proceeds via an anion‐free radical chain mechanism (Scheme 4).…”