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Open AccessEditorial

Editorial to the Organophosphorus Chemistry Special Issue of Molecules (2012–2014)

by György Keglevich

Molecules 2014, 19(10), 15408-15410; https://doi.org/10.3390/molecules191015408 - 26 Sep 2014

Viewed by 4598

Abstract

The review entitled “Organophosphorus Chemistry for the Synthesis of Dendrimers” gives an overview of the methods of synthesis of phosphorus-containing dendrimers, with emphasis on the various roles played by the chemistry of phosphorus [1]. It is demonstrated that the presence of phosphorus atom(s) [...] Read more.

The review entitled “Organophosphorus Chemistry for the Synthesis of Dendrimers” gives an overview of the methods of synthesis of phosphorus-containing dendrimers, with emphasis on the various roles played by the chemistry of phosphorus [1]. It is demonstrated that the presence of phosphorus atom(s) at each branching point of the dendrimeric structure is particularly important and highly valuable. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

Research

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1527 KiB

Open AccessArticle

Palladium-Catalyzed Allylation/Benzylation of H-Phosphinate Esters with Alcohols

by Anthony Fers-Lidou, Olivier Berger and Jean-Luc Montchamp

Molecules 2016, 21(10), 1295; https://doi.org/10.3390/molecules21101295 - 28 Sep 2016

Cited by 11 | Viewed by 7522

Abstract

The Pd-catalyzed direct alkylation of H-phosphinic acids and hypophosphorous acid with allylic/benzylic alcohols has been described previously. Here, the extension of this methodology to H-phosphinate esters is presented. The new reaction appears general, although its scope is narrower than with the [...] Read more.

The Pd-catalyzed direct alkylation of H-phosphinic acids and hypophosphorous acid with allylic/benzylic alcohols has been described previously. Here, the extension of this methodology to H-phosphinate esters is presented. The new reaction appears general, although its scope is narrower than with the acids, and its mechanism is likely different. Various alcohols are examined in their reaction with phosphinylidene compounds R¹R²P(O)H. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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1279 KiB

Open AccessArticle

Practical and Efficient Synthesis of α-Aminophosphonic Acids Containing 1,2,3,4-Tetrahydroquinoline or 1,2,3,4-Tetrahydroisoquinoline Heterocycles

by Mario Ordóñez, Alicia Arizpe, Fracisco J. Sayago, Ana I. Jiménez and Carlos Cativiela

Molecules 2016, 21(9), 1140; https://doi.org/10.3390/molecules21091140 - 31 Aug 2016

Cited by 28 | Viewed by 8142

Abstract

We report here a practical and efficient synthesis of α-aminophosphonic acid incorporated into 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroisoquinoline heterocycles, which could be considered to be conformationally constrained analogues of pipecolic acid. The principal contribution of this synthesis is the introduction of the phosphonate group in [...] Read more.

We report here a practical and efficient synthesis of α-aminophosphonic acid incorporated into 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroisoquinoline heterocycles, which could be considered to be conformationally constrained analogues of pipecolic acid. The principal contribution of this synthesis is the introduction of the phosphonate group in the N-acyliminium ion intermediates, obtained from activation of the quinoline and isoquinoline heterocycles or from the appropriate δ-lactam with benzyl chloroformate. Finally, the hydrolysis of phosphonate moiety with simultaneous cleavage of the carbamate afforded the target compounds. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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4915 KiB

Open AccessArticle

Effect of Mono- and Poly-CH/P Exchange(s) on the Aromaticity of the Tropylium Ion

by Ankita Puri and Raakhi Gupta

Molecules 2016, 21(8), 1099; https://doi.org/10.3390/molecules21081099 - 20 Aug 2016

Cited by 4 | Viewed by 8131

Abstract

In view of the fact that the phosphorus atom in its low co-ordination state (coordination numbers 1 and 2) has been termed as the carbon copy, there have been attempts to investigate, theoretically as well as experimentally, the effect of the exchange(s) of [...] Read more.

In view of the fact that the phosphorus atom in its low co-ordination state (coordination numbers 1 and 2) has been termed as the carbon copy, there have been attempts to investigate, theoretically as well as experimentally, the effect of the exchange(s) of CH- moiety with phosphorus atom(s) (CH/P) on the structural and other aspects of the classical carbocyclic and heterocyclic systems. Tropylium ion is a well-known non-benzenoid aromatic system and has been studied extensively for its aromatic character. We have now investigated the effect of mono- and poly-CH/P exchange(s) on the aromaticity of the tropylium ion. For this purpose, the parameters based on the geometry and magnetic properties, namely bond equalization, aromatic stabilization energies (ASE), Nucleus-Independent Chemical Shift (NICS) values, (NICS(0), NICS(1), NICS(1)_zz), proton nucleus magnetic resonance (¹H-NMR) chemical shifts, magnetic susceptibility exaltation and magnetic anisotropic values of mono-, di-, tri- and tetra-phosphatropylium ions have been determined at the Density Functional Theory (DFT) (B3LYP/6-31+G(d)) level. Geometry optimization reveals bond length equalization. ASEs range from −46.3 kcal/mol to −6.2 kcal/mol in mono- and diphospha-analogues which are planar. However, the ions having three and four phosphorus atoms lose planarity and their ASE values approach the values typical for non-aromatic structures. Of the three NICS values, the NICS(1)_zz is consistently negative showing aromatic character of all the systems studied. It is also supported by the magnetic susceptibility exaltations and magnetic anisotropic values. Furthermore, ¹H-NMR chemical shifts also fall in the aromatic region. The conclusion that mono-, di-, tri- and tetra-phosphatropylium ions are aromatic in nature has been further corroborated by determining the energy gap between the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) (HOMO − LUMO gap), which falls in the range, ca. 3 × 10⁻¹⁹–9 × 10⁻¹⁹ J. The systems having more than four phosphorus atoms are not able to sustain their monocyclic structure. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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863 KiB

Open AccessArticle

Synthesis, Spectral Characterization of Several Novel Pyrene-Derived Aminophosphonates and Their Ecotoxicological Evaluation Using Heterocypris incongruens and Vibrio fisheri Tests

by Jarosław Lewkowski, Maria Rodriguez Moya, Marta Chmielak, Diana Rogacz, Kamila Lewicka and Piotr Rychter

Molecules 2016, 21(7), 936; https://doi.org/10.3390/molecules21070936 - 19 Jul 2016

Cited by 12 | Viewed by 5916

Abstract

Four diphenyl pyrene-derived aminophosphonates were synthesized. Attempts were made to synthesize diphenyl N-(R)-α-methylbenzylamino(pyren-1-yl)methylphosphonate (3e) in order to obtain the chiral aminophosphonate bearing a pyrene moiety. Because these attempts failed, dimethyl and dibenzyl N-(R)-α-methylbenzyl substituted aminophosphonates [...] Read more.

Four diphenyl pyrene-derived aminophosphonates were synthesized. Attempts were made to synthesize diphenyl N-(R)-α-methylbenzylamino(pyren-1-yl)methylphosphonate (3e) in order to obtain the chiral aminophosphonate bearing a pyrene moiety. Because these attempts failed, dimethyl and dibenzyl N-(R)-α-methylbenzyl substituted aminophosphonates 4 and 5 were synthesized and the predominant diastereoisomer of dimethyl aminophosphonate 4 was isolated. The resolution of the diastereomeric mixture of 5 failed. Aminophosphonates 3a–d and the predominant diastereoisomer of 4 were investigated in terms of their ecotoxicity using tests performed on the ostracode Heterocypris incongruens and the fluorescent bacterium Vibrio fisheri. The tests confirmed the moderate-to-high ecotoxicity of aminophosphonates 3a–d and 4, but no evident correlation between the structure and toxicity has been found. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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1796 KiB

Open AccessArticle

The Effect of New Thiophene-Derived Aminophosphonic Derivatives on Growth of Terrestrial Plants: A Seedling Emergence and Growth Test

by Jarosław Lewkowski, Zbigniew Malinowski, Agnieszka Matusiak, Marta Morawska, Diana Rogacz and Piotr Rychter

Molecules 2016, 21(6), 694; https://doi.org/10.3390/molecules21060694 - 30 May 2016

Cited by 11 | Viewed by 5727

Abstract

The aim of this work was to synthesize selected thiophene-derived aminophosphonic systems and evaluate the phytotoxicity of newly obtained products according to the OECD 208 Guideline. Seven new thiophene-derived N-substituted dimethyl aminomethylphosphonic acid esters 2a–h were synthesized by the addition [...] Read more.

The aim of this work was to synthesize selected thiophene-derived aminophosphonic systems and evaluate the phytotoxicity of newly obtained products according to the OECD 208 Guideline. Seven new thiophene-derived N-substituted dimethyl aminomethylphosphonic acid esters 2a–h were synthesized by the addition of an appropriate phosphite to azomethine bond of starting Schiff bases 1a–h, and NMR spectroscopic properties of aminophosphonates were investigated. These eight compounds were analyzed in regard to their phytotoxicity towards two plants, radish (Raphanus sativus) and oat (Avena sativa). On the basis of the obtained results, it was found that tested aminophosphonates 2a–h showed an ecotoxicological impact against selected plants, albeit to various degrees. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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195 KiB

Open AccessArticle

Cs⁺ Removal from Aqueous Solutions through Adsorption onto Florisil^® Impregnated with Trihexyl(tetradecyl)phosphonium Chloride

by Lavinia Lupa, Adina Negrea, Mihaela Ciopec and Petru Negrea

Molecules 2013, 18(10), 12845-12856; https://doi.org/10.3390/molecules181012845 - 16 Oct 2013

Cited by 24 | Viewed by 6194

Abstract

This research determined the adsorption performance of Florisil^® impregnated with trihexyl(tetradecyl)phosphonium chloride (Cyphos IL-101) in the process of Cs⁺ removal from aqueous solutions. The obtained Florisil^® impregnated with the studied ionic liquid was characterized through energy dispersive X-ray analysis and [...] Read more.

This research determined the adsorption performance of Florisil^® impregnated with trihexyl(tetradecyl)phosphonium chloride (Cyphos IL-101) in the process of Cs⁺ removal from aqueous solutions. The obtained Florisil^® impregnated with the studied ionic liquid was characterized through energy dispersive X-ray analysis and Fourier transform infrared spectroscopy in order to verify that the impregnation with the ionic liquid had occurred. The adsorption process has been investigated as a function of pH, solid:liquid ratio, adsorbate concentration, contact time and temperature. The isotherm data was well described by a Langmuir isotherm model. The maximum adsorption capacities of the Florisil^® impregnated with the studied ionic liquid was found to be 3.086 mg Cs⁺/g of adsorbent. The results indicated that the adsorption fitted well with the pseudo-second order kinetic model. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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550 KiB

Open AccessArticle

Hydrophosphonylation of Nanoparticle Schiff Bases as a Mean for Preparation of Aminophosphonate-Functionalized Nanoparticles

by Justyna Siemieniec, Pawel Kafarski and Pawel Plucinski

Molecules 2013, 18(7), 8473-8484; https://doi.org/10.3390/molecules18078473 - 18 Jul 2013

Cited by 9 | Viewed by 5944

Abstract

The development of nanotechnology is responsible for an increase in the achievements in medical diagnostics and in the preparation of new therapeutic vehicles. In particular, magnetic nanoparticles with a modified surface are a very attractive alternative to deliver therapeutic agents. We describe the [...] Read more.

The development of nanotechnology is responsible for an increase in the achievements in medical diagnostics and in the preparation of new therapeutic vehicles. In particular, magnetic nanoparticles with a modified surface are a very attractive alternative to deliver therapeutic agents. We describe the modification of the surface of the iron oxide nanoparticles with aminophosphonic acids by applying the classic hydrophosphonylation approach. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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Review

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13589 KiB

Open AccessReview

Chiral Hypervalent, Pentacoordinated Phosphoranes

by Dorota Krasowska, Jacek Chrzanowski, Piotr Kiełbasiński and Józef Drabowicz

Molecules 2016, 21(11), 1573; https://doi.org/10.3390/molecules21111573 - 21 Nov 2016

Cited by 19 | Viewed by 9052

Abstract

This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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6143 KiB

Open AccessReview

Synthetic Procedures Leading towards Aminobisphosphonates

by Ewa Chmielewska and Paweł Kafarski

Molecules 2016, 21(11), 1474; https://doi.org/10.3390/molecules21111474 - 4 Nov 2016

Cited by 28 | Viewed by 10909

Abstract

Growing interest in the biological activity of aminobisphosphonates has stimulated the development of methods for their synthesis. Although several general procedures were previously elaborated to reach this goal, aminobisphosphonate chemistry is still developing quite substantially. Thus, innovative modifications of the existing commonly used [...] Read more.

Growing interest in the biological activity of aminobisphosphonates has stimulated the development of methods for their synthesis. Although several general procedures were previously elaborated to reach this goal, aminobisphosphonate chemistry is still developing quite substantially. Thus, innovative modifications of the existing commonly used reactions, as well as development of new procedures, are presented in this review, concentrating on recent achievements. Additionally, selected examples of aminobisphosphonate derivatization illustrate their usefulness for obtaining new diagnostic and therapeutic agents. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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7661 KiB

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Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ⁵-oxaphosphetanes

by Anastasy O. Kolodiazhna and Oleg I. Kolodiazhnyi

Molecules 2016, 21(10), 1371; https://doi.org/10.3390/molecules21101371 - 17 Oct 2016

Cited by 6 | Viewed by 6959

Abstract

Results of research into four-membered 2-halo-1,2λ⁵-oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ⁵-oxaphosphetanes by reaction of P-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-сycloaddition of ylides to aldehydes was proposed on the base of low-temperature [...] Read more.

Results of research into four-membered 2-halo-1,2λ⁵-oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ⁵-oxaphosphetanes by reaction of P-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-сycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ⁵-oxaphosphetanes were isolated as individual compounds and their structures were confirmed by ¹Н-, ¹³C-, ¹⁹F- and ³¹Р-NMR spectra. These compounds are convenient reagents for preparing of various organic and organophosphorus compounds hardly available by other methods. Chemical and physical properties of the 2-halo-1,2λ⁵-oxaphosphetanes are reviewed. The 2-chloro-1,2λ⁵-oxaphosphetanes, rearrange with formation of 2-chloroalkyl-phosphonates or convert into trans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ⁵-oxaphosphetanes are analyzed. The 2-halo-1,2λ⁵-oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl- or vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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10942 KiB

Open AccessReview

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

by José Luis Viveros-Ceballos, Mario Ordóñez, Francisco J. Sayago and Carlos Cativiela

Molecules 2016, 21(9), 1141; https://doi.org/10.3390/molecules21091141 - 29 Aug 2016

Cited by 28 | Viewed by 8869

Abstract

α-Amino-C-phosphinic acids and derivatives are an important group of compounds of synthetic and medicinal interest and particular attention has been dedicated to their stereoselective synthesis in recent years. Among these, phosphinic pseudopeptides have acquired pharmacological importance in influencing physiologic and pathologic [...] Read more.

α-Amino-C-phosphinic acids and derivatives are an important group of compounds of synthetic and medicinal interest and particular attention has been dedicated to their stereoselective synthesis in recent years. Among these, phosphinic pseudopeptides have acquired pharmacological importance in influencing physiologic and pathologic processes, primarily acting as inhibitors for proteolytic enzymes where molecular stereochemistry has proven to be critical. This review summarizes the latest developments in the asymmetric synthesis of acyclic and phosphacyclic α-amino-C-phosphinic acids and derivatives, following in the first case an order according to the strategy used, whereas for cyclic compounds the nitrogen embedding in the heterocyclic core is considered. In addition selected examples of pharmacological implications of title compounds are also disclosed. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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3436 KiB

Open AccessReview

Synthesis of Hydroxymethylenebisphosphonic Acid Derivatives in Different Solvents

by Dávid Illés Nagy, Alajos Grün, Sándor Garadnay, István Greiner and György Keglevich

Molecules 2016, 21(8), 1046; https://doi.org/10.3390/molecules21081046 - 11 Aug 2016

Cited by 20 | Viewed by 7275

Abstract

The syntheses of hydroxymethylenebisphosphonic acid derivatives (dronic acid derivatives) starting from the corresponding substituted acetic acids and P-reagents, mainly phosphorus trichloride and phosphorous acid are surveyed according to the solvents applied. The nature of the solvent is a critical point due to the [...] Read more.

The syntheses of hydroxymethylenebisphosphonic acid derivatives (dronic acid derivatives) starting from the corresponding substituted acetic acids and P-reagents, mainly phosphorus trichloride and phosphorous acid are surveyed according to the solvents applied. The nature of the solvent is a critical point due to the heterogeneity of the reaction mixtures. This review sheds light on the optimum choice and ratio of the P-reactants, and on the optimum conditions. Full article

(This article belongs to the Special Issue Recent Advances in Organophosphorus Chemistry)

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981 KiB

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Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

by Vasily P. Morgalyuk

Molecules 2014, 19(9), 12949-13009; https://doi.org/10.3390/molecules190912949 - 25 Aug 2014

Cited by 11 | Viewed by 11410

Abstract

The underinvestigated derivatives of unstable phosphorylated formaldehyde acetals and some of the structurally related compounds, such as thioacetals, aminonitriles, aminomethylphosphinoyl compounds, are considered. Separately considered are halogen aminals of phosphorylated formaldehyde, acetals of phosphorylated formaldehyde of H-phosphinate-type and a phosphorylated gem-diol of formaldehyde. [...] Read more.

The underinvestigated derivatives of unstable phosphorylated formaldehyde acetals and some of the structurally related compounds, such as thioacetals, aminonitriles, aminomethylphosphinoyl compounds, are considered. Separately considered are halogen aminals of phosphorylated formaldehyde, acetals of phosphorylated formaldehyde of H-phosphinate-type and a phosphorylated gem-diol of formaldehyde. Synthetic methods, chemical properties and examples of practical applications are given. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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680 KiB

Open AccessReview

Synthesis of DNA/RNA and Their Analogs via Phosphoramidite and H-Phosphonate Chemistries

by Subhadeep Roy and Marvin Caruthers

Molecules 2013, 18(11), 14268-14284; https://doi.org/10.3390/molecules181114268 - 18 Nov 2013

Cited by 91 | Viewed by 17959

Abstract

The chemical synthesis of DNA and RNA is universally carried out using nucleoside phosphoramidites or H-phosphonates as synthons. This review focuses on the phosphorus chemistry behind these synthons and how it has been developed to generate procedures whereby yields per condensation approach 100% [...] Read more.

The chemical synthesis of DNA and RNA is universally carried out using nucleoside phosphoramidites or H-phosphonates as synthons. This review focuses on the phosphorus chemistry behind these synthons and how it has been developed to generate procedures whereby yields per condensation approach 100% with very few side products. Additionally the synthesis and properties of certain DNA and RNA analogs that are modified at phosphorus will also be discussed. These analogs include boranephosphonates, metallophosphonates, and alkylboranephosphines. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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Open AccessReview

Stoichiometric and Catalytic Synthesis of Alkynylphosphines

by Elise Bernoud, Romain Veillard, Carole Alayrac and Annie-Claude Gaumont

Molecules 2012, 17(12), 14573-14587; https://doi.org/10.3390/molecules171214573 - 7 Dec 2012

Cited by 19 | Viewed by 5714

Abstract

Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, [...] Read more.

Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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Organophosphorus Chemistry for the Synthesis of Dendrimers

by Anne-Marie Caminade, Régis Laurent, Maria Zablocka and Jean-Pierre Majoral

Molecules 2012, 17(11), 13605-13621; https://doi.org/10.3390/molecules171113605 - 16 Nov 2012

Cited by 21 | Viewed by 7494

Abstract

Dendrimers are multifunctional, hyperbranched and perfectly defined macromolecules, synthesized layer after layer in an iterative manner. Besides the nature of the terminal groups responsible for most of the properties, the nature of the internal structure, and more precisely of the branching points, is [...] Read more.

Dendrimers are multifunctional, hyperbranched and perfectly defined macromolecules, synthesized layer after layer in an iterative manner. Besides the nature of the terminal groups responsible for most of the properties, the nature of the internal structure, and more precisely of the branching points, is also of crucial importance. For more than 15 years, we have demonstrated that the presence of phosphorus atom(s) at each branching point of the dendrimeric structure is particularly important and highly valuable for three main reasons: (i) the versatility of phosphorus chemistry that allows diversified organochemistry for the synthesis of dendrimers; (ii) the use of ³¹P-NMR, which is a highly valuable tool for the characterization of dendrimers; (iii) some properties (in the fields of catalysis, materials, and especially biology), that are directly connected to the nature of the internal structure and of the branching points. This review will give an overview of the methods of synthesis of phosphorus-containing dendrimers, as well on the ways to graft phosphorus derivatives as terminal groups, with emphasis on the various roles played by the chemistry of phosphorus. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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Synthesis and Modifications of Phosphinic Dipeptide Analogues

by Artur Mucha

Molecules 2012, 17(11), 13530-13568; https://doi.org/10.3390/molecules171113530 - 15 Nov 2012

Cited by 56 | Viewed by 7548

Abstract

Pseudopeptides containing the phosphinate moiety (-P(O)(OH)CH₂-) have been studied extensively, mainly as transition state analogue inhibitors of metalloproteases. The key synthetic aspect of their chemistry is construction of phosphinic dipeptide derivatives bearing appropriate side-chain substituents. Typically, this synthesis involves a multistep [...] Read more.

Pseudopeptides containing the phosphinate moiety (-P(O)(OH)CH₂-) have been studied extensively, mainly as transition state analogue inhibitors of metalloproteases. The key synthetic aspect of their chemistry is construction of phosphinic dipeptide derivatives bearing appropriate side-chain substituents. Typically, this synthesis involves a multistep preparation of two individual building blocks, which are combined in the final step. As this methodology does not allow simple variation of the side-chain structure, many efforts have been dedicated to the development of alternative approaches. Recent achievements in this field are summarized in this review. Improved methods for the formation of the phosphinic peptide backbone, including stereoselective and multicomponent reactions, are presented. Parallel modifications leading to the structurally diversified substituents are also described. Finally, selected examples of the biomedical applications of the title compounds are given. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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303 KiB

Open AccessReview

The Kabachnik–Fields Reaction: Mechanism and Synthetic Use

by György Keglevich and Erika Bálint

Molecules 2012, 17(11), 12821-12835; https://doi.org/10.3390/molecules171112821 - 1 Nov 2012

Cited by 258 | Viewed by 16704

Abstract

The Kabachnik–Fields (phospha-Mannich) reaction involving the condensation of primary or secondary amines, oxo compounds (aldehydes and ketones) and >P(O)H species, especially dialkyl phosphites, represents a good choice for the synthesis of α-aminophosphonates that are of significant importance due to their biological activity. In [...] Read more.

The Kabachnik–Fields (phospha-Mannich) reaction involving the condensation of primary or secondary amines, oxo compounds (aldehydes and ketones) and >P(O)H species, especially dialkyl phosphites, represents a good choice for the synthesis of α-aminophosphonates that are of significant importance due to their biological activity. In general, these three-component reactions may take place via an imine or an α-hydroxy-phosphonate intermediate. The monitoring of a few Kabachnik–Fields reactions by in situ Fourier transform IR spectroscopy has indicated the involvement of the imine intermediate that was also justified by theoretical calculations. The Kabachnik–Fields reaction was extended to >P(O)H species, comprising cyclic phosphites, acyclic and cyclic H-phosphinates, as well as secondary phosphine oxides. On the other hand, heterocyclic amines were also used to prepare new α-amino phosphonic, phosphinic and phosphine oxide derivatives. In most cases, the synthesis under solvent-free microwave (MW) conditions is the method of choice. It was proved that, in the cases studied by us, there was no need for the use of any catalyst. Moreover, it can be said that sophisticated and environmentally unfriendly catalysts suggested are completely unnecessary under MW conditions. Finally, the double Kabachnik–Fields reaction has made available bis(phosphonomethyl)amines, bis(phosphinoxidomethyl)amines and related species. The bis(phosphinoxidomethyl)amines serve as precursors for bisphosphines that furnish ring platinum complexes on reaction with dichlorodibenzonitriloplatinum. Full article

(This article belongs to the Special Issue Organophosphorus Chemistry)

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