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Organophosphorus pyrrolidine derivatives possessing P–N bonds are a promising yet underexplored class of compounds. In this short review we overview the general approaches to these compounds described so far, with a special emphasis on their asymmetric synthesis. 1 Introduction 2 Synthesis of Pyrrolidine-Based P(III) Derivatives 3 Synthesis of Pyrrolidine-Based P(V) Derivatives 3.1 Phosphorylation of Pyrrolidines with P(V) Acid Chlorides 3.2 Phosphorylation of Pyrrolidines with P(V) Acid Esters 3.3 Syntheses via the Atherton–Todd Reaction 3.4 Oxidation of Pyrrolidine-Based P(III) Derivatives 4 Syntheses of N -Phosphorylpyrrolidines from Acyclic Precursors 5 Conclusions [ABSTRACT FROM AUTHOR]

Pyrrolidine-based phosphonates, analogues of the natural amino acid proline, possess a diverse set of biological activity. The goal of this short review is to summarize the major developments in the synthesis of phosphaproline derivatives reported since 2004 with special emphasis on the mechanisms and limitations of the methods presented. 1 Introduction 2 Phosphorylation of Pyrrolidine Derivatives 2.1 Syntheses via Pudovik Reaction 2.2 Syntheses via Arbuzov Reaction 2.3 Decarboxylative Phosphorylation of Proline 2.4 Direct C–H Bond Phosphorylation 2.5 Other Reactions 2.6 Overview of Phosphorylation Methods 3 Synthesis of 2-Phosphorylpyrrolidines from Acyclic Precursors 3.1 Cyclization of 4-Substituted Butylamine Derivatives 3.2 [3+2]-Dipolar Cycloaddition of α-Iminophosphonates 3.3 Cyclization of Aminoalkynes and 4-Aminocarbonyl Compounds 4 Conclusions [ABSTRACT FROM AUTHOR]

A new approach to the synthesis of spirophosphoranes 9, 11, 15a-c containing P-C, P-O, and P-N intramolecular bonds was developed. It is based on the reaction of trivalent phosphorus acid amides with bis(o-hydroxyaryl)diimines. The composition and structure of the products obtained were confirmed by NMR methods, IR spectroscopy, elemental analysis and X-ray analysis. [ABSTRACT FROM AUTHOR]

Phosphorylation of 1,3-bis(2-hydroxyethoxy)benzene and octa(2-hydroxyethyl) calix[4]-resorcinarenes with P(III) acid amides and chloramides has been studied. It has been determined that the nature of phosphorous acid amides affects significantly the synthetic result of the reaction. [ABSTRACT FROM AUTHOR]

The presented mini-review summarizes the results of our study of the condensation of resorcinol and its derivatives with phosphorylated acetals, aldehydes, and vinylphosphonates with an aim to prepare new calix[4]resorcinols (thio)phosphorylated on the lower rim of macromolecule. The properties of the synthesized macrocyclic compounds are studied and some aspects of their possible application are considered. [ABSTRACT FROM AUTHOR]

We synthesized new phosphorus-containing linear and macrocyclic polyphenols using organic compounds containing phosphorus-carbon bonds and the phosphorus atom of various coordination, and also with reactive acetal, aldehyde, vinylethoxy, and methylene quinone fragments as starting materials. These achievements are briefly summarized. [ABSTRACT FROM AUTHOR]

Interaction of cyclic derivatives of pyridoxal (1-ethoxy- and 1-diethylaminofuropyridines) with chlorides of phosphoric and carboxylic acids is carried out with the participation of phenolic hydroxyl pyridoxal. Depending on the reaction conditions in the case of aminofuropyridine, the formation of phosphorylated aminofuropyridines and hydroxyfuropyridines is possible. [ABSTRACT FROM AUTHOR]

A new approach to the synthesis of spirophosphoranes was developed. It is based on the reaction of hexamethyltriamidophosphite with bis(o-hydroxyaryl)diimines. [ABSTRACT FROM PUBLISHER]

A new approach to the synthesis of polycyclic hexacoordinated phosphorus derivatives was developed. It is based on the reaction of alkylene chlorophosphites with salicylaldehyde diimines without a base catalyst. [ABSTRACT FROM AUTHOR]

New O-phosphorylated pyridoxal derivatives, based on the azomethine reaction with acid chlorides P(IV) were synthesized. Depending on the nature of the substituent on the nitrogen atom final products are phosphorylated furopyridines or azomethines of pyridoxal. [ABSTRACT FROM PUBLISHER]

Perdithiophosphonic acids are new types of tetracoordinated phosphorus thioacids bearing many dithiophosphoryl groups. Novel perdithiophosphonic acids were obtained by the reactions of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides with hydroxyphenols such as resorcinol, 4,4'-iso-propylidenebisphenol, pyrogallol, and calix[4]resorcinols. [ABSTRACT FROM AUTHOR]

New phosphorylated azomethines on the basis of salicylaldehyde were obtained. These compounds react with P(Y) chlorides to form diphosphorylated azomethines. [ABSTRACT FROM PUBLISHER]

The products of carbonyl phosphonylation of pyridoxal with alkylphosphinic acid ethyl esters, phosphorous acid dialkyl esters have been obtained for the first time. In some cases, the products of addition are hydrolytically unstable and stabilize by forming internal betaine structures. The reaction of pyridoxal with phosphorous acid in alcohol solutions gives alkoxyfuropyridines possessing the iminium nitrogen atom. [ABSTRACT FROM PUBLISHER]

Calix[4]resorcinols containing four [N-diethoxyphosphorylmethyl-N-(2,2-dimethoxyethyl)amino]methyl substituents at the upper rim of molecule were synthesized by condensation of calix[4]resorcinols with formaldehyde and diethyl N-(2,2-dimethoxyethyl)- aminomethylphosphonate. [Copyright &y& Elsevier]

Thiophosphorylated derivatives of meta - and ortho -hydroxybenzaldehydes take part in one-step, acid-catalyzed condensations with resorcinol and its derivatives. As a result, new calix[4]resorcinols, which contain four 2-thioxo-1,3,2-dioxaphosphorinane fragments on the aromatic substituents of the calixarene matrix, have been synthesized. In this case, macrocyclic products are formed as rccc - ( cone or boat conformation) and/or rctt - ( chair conformation) diastereomers, the ratio of which depends on the structure of the starting reagents. The obtained products have been isolated and their structures determined by NMR methods and single-crystal X-ray diffraction. The spectral differences of conformational isomers of the prepared macrocycles have been demonstrated. [ABSTRACT FROM AUTHOR]

Abstract: Novel calix[4]resorcinols with four 2-thioxo-1,3,2-dioxaphosphorinane fragments included in aromatic substituents have been synthesized via a one-step condensation of resorcinol and its derivatives with a new para-thiophosphorylated benzaldehyde. It has been found that the diastereomeric ratio depends substantially on the reaction conditions, in particular, the solvents and catalysts used. The macrocyclic products obtained are rctt- and/or rccc-isomers, which were isolated and the structures determined by NMR and single crystal X-ray diffraction studies. [Copyright &y& Elsevier]

A novel one-pot method for the preparation of N-substituted 2-phopshorylpyrrolidines from readily available 4,4-diethoxybutan-1-amine derivatives and P (III) acid chlorides is described. The presented method benefits from simple reaction and work-up procedures, mild reaction conditions, avoids protecting group introduction-removal stages and provides a straightforward access to target compounds. In vitro cytotoxicity studies indicate that obtained 2-phopshorylpyrrolidines inhibit selectively M-Hela tumor cells growth. The activity of some derivatives towards M-Hela and MCF-7 tumor cells is comparable to that of reference drug Tamoxifen. In contrast to Tamoxifen and Doxorubicin tested compounds have no cytotoxic effects on normal cells. Image 1 • A novel method of synthesis of N-substituted 2-phopshorylpyrrolidines is developed. • Some of obtained 2-phopshorylpyrrolidines inhibit M-Hela and MCF-7 tumor cells growth. • In contrast to Tamoxifen and Doxorubicin tested compounds do not affect normal cells. [ABSTRACT FROM AUTHOR]