34860-03-2Relevant academic research and scientific papers
Solvent effects in deamination reactions
Banert, Klaus,Bunse, Michael,Engbert, Theodor,Gassen, Karl-Rudolf,Kurnianto, Apriana W.,Kirmse, Wolfgang
, p. 272 - 278 (2007/10/02)
Nitrous acid deaminations of (S)-2-butanamine, (2R,3S)-3-methyl-2-pentanamine (8), cyclopropananmine (17) and 4,4-dimethyl-2-adamantanamine (30) have been studied in water and in a series of carboxylic acids of decreasing polarity (acetic, 3,3-dimethylbutyric, 2-ethylhexanoic acid).The stereochemistry of aqueous deaminations varies from predominant inversion to predominant retention, depending upon the structure of the substrate (steric hindrance, neighbouring-group participation, etc.).In carboxylic acid media, alcohols arise with predominant retention, i.e. by front-side attack of the "internal" nucleophile (water).Inverting displacement of nitrogen by the "external" nucleophile (carboxylic acid/carboxylate) increases with decreasing polarity of the solvent.Even cyclopropanamine yields cyclopropyl esters (2-10percent) of inverted configuration, as shown with the aid of deuterium labels.Current mechanistic concepts are modified to account for these results.
