Donor-Acceptor N → P Interaction and its Effect on the Phosphorylation of α-Aminoketones

Abstract

Aminovinylphosphites of Z-configuration R₂″PO-CR═CH-NR₂' are formed in the reaction of α-aminoketones RCOCH₂NR₂' and chlorophosphites with the use of triethylamine as a base. The high stereoselectivity of this process is due to the preliminary coordination of phosphorus chloride to the amino group of the substrate and the following intramolecular rearrangement in the complex with the simultaneous evolution of the salt of hydrogen chloride with triethylamine. A thermodynamic study of the complex formation between reactants in the first stage of the above mentioned process supports this idea.

Key Words:

• α-Aminoketones
• aminovinylphosphites
• N → P donor-acceptor interaction
• thermodynamic parameters