Comparative Studies on the Amidoalkylating Properties of N-(1-Methoxyalkyl)Amides and 1-(N-Acylamino)Alkyltriphenylphosphonium Salts in the Michaelis-Arbuzov-Like Reaction: A New One-Pot Transformation of N-(1-Methoxyalkyl)Amides into Phosphonic or Phosphinic Analogs of N-Acyl-α-Amino Acids

• Published in: Phosphorus, sulfur, and silicon and the related elements sulfur, and silicon and the related elements, 2013-07, Vol.188 (7), p.967-980
• Main Authors: Adamek, Jakub, Październiok-Holewa, Agnieszka, Zielińska, Katarzyna, Mazurkiewicz, Roman
• Format: Article
• Language: English
• Subjects: 1-(N-acylamino)alkyltriphenylphosphonium salts; Amidoalkylating agents; Michaelis-Arbuzov-like reaction; N-(1-methoxyalkyl)amides; phosphorus analogs of N-acyl-α-amino acids
• ISSN: 1042-6507; 1563-5325
• DOI: 10.1080/10426507.2012.729237

It was demonstrated that N-(1-methoxyalkyl)amides do not react with trimethyl phosphite under neutral or basic conditions. The treatment of N-(1-methoxyalkyl)amides with trialkyl phosphites or dialkyl phosphonites, triphenylphosphonium tetrafluoroborate, and Hünig's base caused immediate formation of the corresponding 1-(N-acylamino)-alkyltriphenylphosphonium tetrafluoroborates, followed by the slow Michaelis-Arbuzov-like reaction of phosphonium salt with phosphites or phosphonites to α-(N-acylamino)-alkanephosphonic or α-(N-acylamino)alkanephosphinic acid esters, respectively. A plausible mechanism of the considered transformations, assuming an equilibrium between N-(1-alkoxyalkyl)amide, triphenylphosphonium tetrafluoroborate, 1-(N-acylamino)alkyltriphenyl-phosphonium salt, N-acylimine, and N-acyliminium salts, is discussed.