The synthesis of novel N-heterocyclic α-diphenylphosphinoglycines

Synthetic amino acids are of interest in various fields of chemistry, biochemistry and pharmacy. The first experiments with a phosphanyl group were obtained by condensation of natural amino acids with secondary phosphanes and formaldehyde, usually forming bis(phosphanylmethyl) amino acids, and studied with respect to their use as ligands in rhodium-catalysed hydrogenation reactions and in complexes for radio-diagnostics. The use of primary phosphanes extended the range of N-phosphanylmethyl amino acids to various P,N-heterocyclic types. The incorporation of P-alkyl instead of Pphenyl groups led to an increase in the sensitivity of Nalkyl-α-phosphanylglycines. To obtain more stable α-phosphanyl amino acids we systematically varied the nitrogen substituents of the (diphenylphosphanyl)glycines and report here on the novel N-aryl derivatives 1, their synthesis, structure and properties, and the first examples of their transitionmetal complexes and their use in homogeneous catalysis.

A three-component one-pot reaction of diphenylphosphine, primary amine and glyoxylic acid hydrate in diethyl ether or methanol allowed an easy access to N-monosubstituted diphenylphosphinoglycines 1b-10b.

Electrochemical reactions of white phosphorus with carbonyl compounds

Current project is aimed at the investigation of in situ electrochemical reactions of white phosphorus with organic substrates, such as carbonyl compounds (aliphatic, cyclic and aromatic ketones, aliphatic and aromatic aldehydes). These reactions lead to the formation of new phosphorous intermediates which can be important for synthesis of new organometallic compounds with P-C and P-H bonds. The proposed methods are based on previously investigated phosphorus compound – phosphine oxide H 3 PO, which can be prepared directly from white phosphorus P 4 by mild anodic oxidation of electrochemically generated phosphine PH 3 as it has been shown in our previous works.

Electrochemical synthesis of organonickel sigma-complexes

The electrochemical reduction of [NiBr2(bpy)] (bpy is 2,2'-bipyridine) complex in the presence of aryl bromide in undivided electrochemical cell supplied with a sacrificial nickel anode results in the one-pot formation of an organonickel complex [NiBr(aryl)(bpy)]

 

 

 

 

 

 

 

 

 

Electrochemical generation of phosphine oxide

The electrochemical generation of H3PO was performed in a single electrochemical cell with a lead cathode and a sacrificial zinc anode using P4 melted in a slightly acidic water/ethanol solution (2:1 volume ratio, water acidified with HCl, 2m) at 60 C. The overall electrochemical process may be divided in two parts. In the first step, the electrochemical generation of PH3 on the lead cathode takes place as previously described, while in the second step, mild oxidation of PH3 to H3PO occurs at the anodic surface of the zinc electrode. In agreement with cyclic voltammetry experiments showing an irreversible oxidation wave, PH3 is electrochemically active in the anodic potential range +0.80–1.25 V (vs. Ag/AgNO3, 0.01m in HCN3) and can be therefore oxidized in acidic  ater/ethanol 2:1 solution to H3PO shows the overall electrochemical process resulting in the cathodic reduction of P4 to PH3 and anodic oxidation of PH3 to H3PO (E=+1.24 V vs. Ag/AgNO3, 0.01m in CHCN3).

 

 

 

 

 

 

 

 

 

 

 

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A.E. Arbuzov Institute of Organic and Physical Chemistry

Federal Research Center

Kazan Scientific Center of Russian Academy of Sciences

Arbuzov str., 8

420088  Kazan, Russian Federation

Kazan Federal University

A.M.Butlerov Institute of Chemistry

Kremlyovskaya str., 18

420008 Kazan, Russian Federation

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E-mail: yakhvar@iopc.ru

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