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Recent Development of Organophosphorus Chemistry
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Recent Development of Organophosphorus Chemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (29 February 2024) | Viewed by 6517

Special Issue Editors

Prof. Dr. Dobromir Enchev

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Guest Editor
Department of Organic Chemistry and Technology, Konstantin Preslavsky University of Shumen, Shumen, Bulgaria
Interests: synthesis and properties of cyclic organophosphorus compounds
Prof. Dr. György Keglevich

E-Mail Website
Guest Editor
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1521 Budapest, Hungary
Interests: organophosphorus chemistry; P-heterocycles; phosphonic and phosphinic derivatives; bisphosphonates; green chemistry; microwave assistance; ionic liquids; catalysts; solvent-free reactions; P-C couplings; flow chemistry; pharmaceutical developments
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Organophosphorus compounds not only widely exist in biologically active pharmaceuticals and agrochemicals, but also have widespread applications in material science and organic synthesis as ligands for transition metal complexes. They are currently the subjects of intensive study. Consequently, the advances in organophosphorus chemistry need to be reviewed on a continuous basis, because this chemistry forms an integrant part of modern synthetic organic chemistry. One of the mainstreams for the development in this field is the creation of biologically active organophosphorus compounds that are searched and used as drugs or plant-protecting agents, which leads to the elaboration of advanced methods and monitoring, yielding up-to-date approaches to perform synthesis in an environmentally friendly manner.

Organophosphorus (OP) chemistry has become an integral part of synthetic organic chemistry. OP compounds are used as starting materials, reagents, catalysts (phase transfer catalysts or P(III)-transition metal complexes) and solvents (ionic liquids (ILs)) in research laboratories and in industry. Some of these applications are in the focus today. There are many frequently used reactions, such as reductions, the Wittig reaction and its variations, the Arbuzov reaction, the Mitsunobu reaction etc., that apply P-containing reagents. Other reactions (e.g., homogeneous catalytic transformations, C-C coupling reactions) involve P-ligands in the catalysts. There has been enormous development in the field of chiral OP compounds. Methods have been elaborated for the resolution of tertiary phosphine oxides and for stereoselective OP transformations. The optically active P(III) species may be used in transition metal (Pt, Pd, etc.) complex catalysts, promoting enantioselective transformations. The heterocyclic discipline may include P-heterocycles and classical O- and N-heterocycles with P-functions. A special field comprises P-containing macrocycles and other macromolecules such as dendrimers. A current trend in the OP field is environmentally friendly synthesis. This may include the use of microwave technologies. OP species (e.g., catalysts and ILs) may also be tools in general synthetic organic chemistry. Monitoring the reactions in order to optimize the conditions or to observe reactive species is challenging. Theoretical calculation within OP chemistry is also a developing field; stereostructures and mechanisms can now be easily evaluated. A very important segment of OP chemistry, indeed a driving force of the development, is the pool of biologically active OP compounds that are searched and used as drugs or plant protecting agents. The natural analogue P-compounds (e.g., peptide and amino acid analogues) should also be mentioned. Many new phosphine oxides, phosphinates, phosphonates and phosphoric esters have been described that may find application on a broad scale.

Prof. Dr. Dobromir Enchev
Prof. Dr. György Keglevich
Guest Editors

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Keywords

  • organophosphorus compounds
  • environmentally friendly syntheses
  • applications
  • natural analogue P-compounds

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Published Papers (5 papers)

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Research

13 pages, 3119 KiB  
Article
Novel Bicyclic P,S-Heterocycles via Stereoselective hetero-Diels–Alder Reactions of Thiochalcones with 1-Phenyl-4H-phosphinin-4-one 1-Oxide
by Grzegorz Mlostoń, Katarzyna Urbaniak, Marcin Palusiak, Elżbieta Łastawiecka, Sławomir Frynas, Kazimierz Michał Pietrusiewicz and Heinz Heimgartner
Molecules 2024, 29(9), 2036; https://doi.org/10.3390/molecules29092036 - 28 Apr 2024
Viewed by 898
Abstract
Thiochalcones undergo cycloaddition reactions in THF solution at 60 °C with the synthetically unexplored 1-phenyl-4H-phosphinin-4-one 1-oxide in a highly regio- and stereoselective manner, yielding hitherto unknown bicyclic P,S-heterocycles containing fused thiopyran and phosphinine rings. The stereochemical structures of [...] Read more.
Thiochalcones undergo cycloaddition reactions in THF solution at 60 °C with the synthetically unexplored 1-phenyl-4H-phosphinin-4-one 1-oxide in a highly regio- and stereoselective manner, yielding hitherto unknown bicyclic P,S-heterocycles containing fused thiopyran and phosphinine rings. The stereochemical structures of two of the obtained (4+2)-cycloadducts were unambiguously assigned by means of the X-ray single-crystal analysis. Based on these assignments, a concerted mechanism of the hetero-Diels–Alder reaction via the preferred endo approach of the heterodiene from the less hindered P=O side of the phosphininone molecule is postulated to explain the established rac-(4RS,8SR,9SR,10SR)-configured (4+2)-cycloadducts isolated as major products. Full article
(This article belongs to the Special Issue Recent Development of Organophosphorus Chemistry)
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16 pages, 3031 KiB  
Article
Design, Synthesis, and Evaluation of B-(Trifluoromethyl)phenyl Phosphine–Borane Derivatives as Novel Progesterone Receptor Antagonists
by Yu Miyajima, Kotaro Ochiai and Shinya Fujii
Molecules 2024, 29(7), 1587; https://doi.org/10.3390/molecules29071587 - 2 Apr 2024
Viewed by 1108
Abstract
We previously revealed that phosphine–boranes can function as molecular frameworks for biofunctional molecules. In the present study, we exploited the diversity of available phosphines to design and synthesize a series of B-(trifluoromethyl)phenyl phosphine–borane derivatives as novel progesterone receptor (PR) antagonists. We revealed [...] Read more.
We previously revealed that phosphine–boranes can function as molecular frameworks for biofunctional molecules. In the present study, we exploited the diversity of available phosphines to design and synthesize a series of B-(trifluoromethyl)phenyl phosphine–borane derivatives as novel progesterone receptor (PR) antagonists. We revealed that the synthesized phosphine–borane derivatives exhibited LogP values in a predictable manner and that the P–H group in the phosphine–borane was almost nonpolar. Among the synthesized phosphine–boranes, which exhibited PR antagonistic activity, B-(4-trifluoromethyl)phenyl tricyclopropylphosphine–borane was the most potent with an IC50 value of 0.54 μM. A docking simulation indicated that the tricyclopropylphosphine moiety plays an important role in ligand–receptor interactions. These results support the idea that phosphine–boranes are versatile structural options in drug discovery, and the developed compounds are promising lead compounds for further structural development of next-generation PR antagonists. Full article
(This article belongs to the Special Issue Recent Development of Organophosphorus Chemistry)
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22 pages, 3283 KiB  
Article
Structure of Tris[2-(4-pyridyl)ethyl]phosphine, Tris[2-(2-pyridyl)ethyl]phosphine, and Their Chalcogenides in Solution: Dipole Moments, IR Spectroscopy, and DFT Study
by Anastasiia A. Kuznetsova, Denis V. Chachkov, Natalia A. Belogorlova, Svetlana F. Malysheva and Yana A. Vereshchagina
Molecules 2024, 29(1), 110; https://doi.org/10.3390/molecules29010110 - 23 Dec 2023
Cited by 1 | Viewed by 1147
Abstract
Tris(hetaryl)substituted phosphines and their chalcogenides are promising polydentate ligands for the design of metal complexes. An experimental and theoretical conformational analysis of tris[2-(4-pyridyl)ethyl]phosphine, tris[2-(2-pyridyl)ethyl]phosphine, and their chalcogenides was carried out by the methods of dipole moments, IR spectroscopy and DFT B3PW91/6-311++G(df,p) calculations. In [...] Read more.
Tris(hetaryl)substituted phosphines and their chalcogenides are promising polydentate ligands for the design of metal complexes. An experimental and theoretical conformational analysis of tris[2-(4-pyridyl)ethyl]phosphine, tris[2-(2-pyridyl)ethyl]phosphine, and their chalcogenides was carried out by the methods of dipole moments, IR spectroscopy and DFT B3PW91/6-311++G(df,p) calculations. In solution, these compounds exist as an equilibrium of mainly non-eclipsed (synclinal or antiperiplanar) forms with a predominance of a symmetrical conformer having a gauche-orientation of the Csp3–Csp3 bonds of pyridylethyl substituents relative to the P=X bond (X = lone pair, O, S, Se) and a gauche-orientation of the pyridyl rings relative to the zigzag ethylene bridges. Regardless of the presence and nature of the chalcogen atom (oxygen, sulfur, or selenium) in the studied molecules with many axes of internal rotation, steric factors—the different position of the nitrogen atoms in the pyridyl rings and the configuration of ethylene bridges—determine the realization and spatial structure of preferred conformers. Full article
(This article belongs to the Special Issue Recent Development of Organophosphorus Chemistry)
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10 pages, 2140 KiB  
Article
Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
by Kyzgaldak Ramazanova, Anna Karina Müller, Peter Lönnecke, Oldamur Hollóczki, Barbara Kirchner and Evamarie Hey-Hawkins
Molecules 2023, 28(20), 7163; https://doi.org/10.3390/molecules28207163 - 19 Oct 2023
Cited by 1 | Viewed by 1033
Abstract
The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by [...] Read more.
The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by sulfurization of the phosphorus atom, thus efficiently blocking the lone pair of electrons, as exemplified for 6b yielding structurally characterized 8b. Additionally, the influence of the substituent in the α position to the phosphorus atom (H, Ph, 2-py, CN) on the reversibility of the reaction was studied. Extensive theoretical calculations for understanding the ring-closing mechanism suggested that a multi-step reaction with one or more intermediates was most probable. Full article
(This article belongs to the Special Issue Recent Development of Organophosphorus Chemistry)
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15 pages, 8839 KiB  
Article
A Study of the Bisphosphonic Derivatives from the Pudovik Reaction of Dialkyl α-Oxophosphonates and >P(O)H Reagents: X-ray Structure and Bioactivity
by Zsuzsanna Szalai, Boldizsár Tóth, Rita Oláhné Szabó, Szilvia Bősze, Konstantin Karaghiosoff, Mátyás Czugler, László Drahos and György Keglevich
Molecules 2023, 28(16), 6037; https://doi.org/10.3390/molecules28166037 - 12 Aug 2023
Cited by 1 | Viewed by 1526
Abstract
New hydroxy-methylenebisphosphonic derivatives were prepared with different P-functions. The outcome of the reaction of α-oxophosphonates (YC(O)P(O)(OR)2) and dialkyl phosphites or diarylphosphine oxides depended on the Y substituent of the oxo-compound, the nature of the P-reagent and the amount of the diethylamine [...] Read more.
New hydroxy-methylenebisphosphonic derivatives were prepared with different P-functions. The outcome of the reaction of α-oxophosphonates (YC(O)P(O)(OR)2) and dialkyl phosphites or diarylphosphine oxides depended on the Y substituent of the oxo-compound, the nature of the P-reagent and the amount of the diethylamine catalyst. Starting from dimethyl α-oxoethylphosphonate, in the presence of 5% of diethylamine, the corresponding Pudovik adduct was the single product. While using 40% of the catalyst, the rearranged species with the >P(O)–O–CH–P(O)< skeleton was the exclusive component. A similar reaction of α-oxobenzylphosphonate followed the rearrangement protocol. X-ray crystallography revealed not only the spatial structures of the three products, but also an intricate pattern evolving from the interplay of slight chemical differences, solvent inclusion and disorder as well as H-bridge patterns, which invite further investigation. In vitro activity of the compounds was assessed on different tumor cell cultures using end-point-type cell tetrazolium-based measurements. These structure–activity studies revealed a cytostatic effect for four rearranged derivatives containing aromatic units. One of them had a pronounced effect on MDA-MB 231 and Ebc-1 cells, showing IC50 = 37.8 and 25.9 µM, respectively. Full article
(This article belongs to the Special Issue Recent Development of Organophosphorus Chemistry)
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