Deamination of 1-Aminoalkylphosphonic Acids: Reaction Intermediates and Selectivity

Abstract

Deamination of 1-aminoalkylphosphonic acids in the reaction with HNO2 (generated “in situ” from NaNO2) yields a mixture of substitution products (1-hydroxyalkylphosphonic acids), elimination products (vinylphosphonic acid derivatives), rearrangement and substitution products (2-hydroxylkylphosphonic acids) as well as H3PO4. The variety of formed reaction products suggests that 1-phosphonoalkylium ions may be intermediates in such deamination reactions.

α-Amido sulphones as useful intermediates in the preparation ofC-chiral α-aminophosphonates and α-aminophosphonic acids

“…Our interest in the preparation of new α-aminophosphonic acids and their esters [36][37][38][39][40] prompted us to investigate the utility of α-amido sulphones as stable imine surrogates and practical intermediates in the preparation of these compounds. Herein we present the results of our research on the preparation of α-aminophosphonic acids and their esters not only as racemic mixtures but also in a highly diastereoselective fashion using a one-pot, effective and simple methodology based on the in situ generation of N-acylimines and their reaction with phosphorus nucleophiles (Scheme 1d).…”

Special Issue “Organophosphorus Chemistry: A New Perspective”

“…The other articles are related to phosphonate compounds, their synthesis, reactivity, and biological properties [ 12 , 13 , 14 , 15 , 16 ]. Moilanen et al prepared an interesting review article about the applications of α-aminophosphonates, -phosphinates, and -phosphine oxides as extraction and precipitation agents for rare earth metals, thorium, and uranium [ 12 ].…”

“…Some future perspectives related to the tunability of the solubility and coordination affinity of the α-amino-functionalized organophosphorus compounds were also discussed. Olszewski et al described the deamination of 1-aminoalkylphosphonic acids in reaction with HNO 2 [ 13 ]. Mechanistic research and analysis of the obtained products allowed the authors to propose a plausible mechanism reaction with the formation of 1-phosphonoalkylium ions as reactive intermediates.…”