Ekaterina V. Matveeva

A Practical and Efficient Green Synthesis of β-Aminophosphoryl Compounds via the Aza-Michael Reaction in Water

Abstract Application of water as a solvent (without any cosolvent) promotes the aza-Michael reaction of diethyl vinylphosphonate and diphenylvinylphosphine oxide with a wide range of N-nucleophiles. The solubility of the starting phosphorus substrate in water does not play a crucial role in the reaction course, decreasing to some extent the reaction rate. The reaction can be performed either at room temperature or under reflux to afford the corresponding β-aminophosphonates and β-aminophosphine oxides in excellent yields and of high purity via a simple freeze-drying isolation procedure. Application of basic catalysts makes possible the addition of weak nucleophiles such as α-amino acids and their phosphorus analogues; that is, α-aminophosphonic acids. The aqueous aza-Michael reaction allowed us to easily perform double phosphorylation of primary amines including polyamines using a reactant ratio (phosphorus substrate: amine) of 2:1.

Synthetic Approaches to Cytotoxic Amidophosphates, Aminophosphonates, and Aminobisphosphonates with 3,5-Bis(arylidene)piperid-4-one Framework

Abstract Facile synthetic approaches to a few novel classes of amidophosphates, ω-aminophosphonates, and bisphosphonates having a 3,5-bis(arylidene)piperid-4-one backbone have been elaborated starting from piperid-4-ones functionalized with phosphorus motives followed by aldol-crotonic condensation with a range of (hetero)aromatic aldehydes or via introduction of the corresponding phosphorus function into the preformed NH-3,5-bis(arylidene)piperid-4-ones. Combination of phosphorus-containing moieties possessing inherent bioactivity and cytotoxic 3,5-bis(arylidene)piperid-4-one moiety resulted in the compounds with high antitumor activity towards human carcinoma cell lines Caov3, A549, Scov3, PC3, KB 3-1, and KB 8–5 (IC50 in the range of 1–80 μM).

Advantages of Organophosphorus Synthesis in Ionic Liquids: “Green” Approaches to Useful Phosphorus-Substituted Building Blocks

Novel examples concerning the application of ionic liquids as a promoting reaction media in organophosphorus chemistry are discussed. Imidazolium ionic liquids were found to accelerate the Michaelis-Arbuzov reaction allowing to perform it under very mild conditions. Both phosphonium and imidazolium ILs give the possibility to perform easily direct amidation of phosphoryl acetic acids by various amines. Nucleophilic displacement reactionin a series of bromoalkylphosphonates was carried out in quantitative yield to afford azidoalkylphosphonates using the [bmim][PF6]/H2O system.

First Phosphorus Functionalized Clathrochelate Iron(II) α-Dioximates

Abstract Clathrochelate Iron(II) α-Dioximates containing macrocyclic bicursors undergo a smooth phosphorylation reaction to yield (thio)phosphorylated monoribbed-functionalized iron(II) mono- and bis-clathrochelates GRAPHICAL ABSTRACT

Extraction Properties of Oligodentate Carbamoylmethylphosphine Oxidesand β-Aminophosphine Oxides Toward Lanthanides and Rhenium(VII)

Abstract The extraction properties of a series of carbamoylmethylphosphine oxides and β-aminophosphine oxides with lanthanide metal ions is presented. Tris[bis(2-diphenyl- phosphorylethyl)-aminoethyl]amine is shown to be highly effective for extraction of Re(VII). GRAPHICAL ABSTRACT