The application and development of green chemical tools - the accomplishment of organophosphorus reactions under green chemical conditions  Page description

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Details of project

  
Identifier
83118
Type K
Principal investigator Keglevich, György
Title in Hungarian A zöldkémia eszköztárának alkalmazása és fejlesztése - szerves foszforkémiai reakciók megvalósítása környezetbarát körülmények között
Title in English The application and development of green chemical tools - the accomplishment of organophosphorus reactions under green chemical conditions
Keywords in Hungarian zöldkémia, foszforkémia, mikrohullám, katalizátor, optimalizálás
Keywords in English green chemistry, organophosphorus chemistry, microwave, catalyst, optimalization
Discipline
Organic, Biomolecular, and Pharmaceutical Chemistry (Council of Physical Sciences)100 %
Ortelius classification: Organic chemistry
Panel Chemistry 2
Department or equivalent Department of Organic Chemistry and Technology (Budapest University of Technology and Economics)
Participants Bálint, Erika
Csontos, István
Drahos, László
Grün, Alajos
Körtvélyesi, Tamás
Ludányi, Krisztina
Szöllősy, Áron
Ujj, Viktória
Starting date 2011-08-01
Closing date 2016-01-31
Funding (in million HUF) 24.000
FTE (full time equivalent) 9.97
state closed project
Summary in Hungarian
A pályázat témája egyrészt a környezetbarát (zöld) kémia eszköztárának alkalmazása különféle reakciók – elsősorban foszfororganikus reakciók – megvalósítása során. Ide tartozik a mikrohullámú (MW) besugárzás jótékony hatásának (pl. hatékonyság és szelektív reakciómegvalósítás) feltárása. Különösen érdekes az olyan új reakciók felkutatása, amelyek hagyományos melegítésre nem is játszódnak le (speciális MW effektus). Vizsgáljuk az oldószermentes megvalósíthatóság és az ionos oldószerek alkalmazásának lehetőségeit, továbbá hasznosítani szeretnénk a MW és a fázistranszfer katalitikus technika együttes alkalmazásából adódó előnyöket (szinergizmus). Másrészt optikailag aktív P-ligandok (5-, 6- és 7-tagú P-heterociklusok) szintézisével ill. ezek megfelelő platina-komplexekké alakításával bővíteni kívánjuk a zöldkémia eszköztárát. Az átmeneti fémkomplexek ugyanis potenciális katalizátorok. A zöldkémia 12 törvényével van összhangban a különféle reakciók in situ FT IR spektroszkópiával, mint on-line módszerrel való monitorálása ill. optimalizálása.
A projekt eredményeképpen a napjainkban igen időszerű környezetbarát diszciplína fejlődéséhez fogunk hozzájárulni módszerek, valamint hatékony és szelektív reakciók ill. új katalizátorok kidolgozásával. Évente legalább 4 nemzetközi folyóirtcikket igérünk a szakterület elismert periodikáiban.
Summary
The purpose of this application, on the one hand, is the application of green chemical tools in the accomplishment of organic reactions, especially within organophosphorus chemistry. One of the lines is to explore the beneficial effects (e.g. efficiency and selectivity) of microwave (MW) irradiation. It is a challenge to explore MW assisted organic reactions that do not take place on traditional thermal heating (special MW effect). We wish to investigate the possibilities for the accomplishment of solventless reactions and for the application of ionic liquids. The possible advantages (e.g. synergism) from the combined use of the MW and the phase transfer catalytic technique are to be studied. On the other hand, we wish to expand the tools of green chemistry by the synthesis of optically active P-ligands (5-, 6- and 7-membered P-heterocycles) and by their transformation to the corresponding platinum complexes that are potential catalysts. Monitoring and optimizing organic reactions by in situ FT IR spectroscopy as an on-line method is also in accord with the 12 principles of green chemistry.
The results of the project will contribute to the development of the discipline of environmentally-friendly chemistry that has a great deal of actuality these days. We shall elaborate efficient and selective methods and new catalysts. We plan to publish at least 4 papers international journals of the field.




 

Final report

  
Results in Hungarian
A projekt során környezetbarát módszereket alkalmaztunk szerves foszforkémiai reakciók megvalósítása során. Törekedtünk az atomhatékonyságra, a veszélyes és környezetkárosító, valamint drága reagensek, katalizátorok és oldószerek kiváltására, a minél rövidebb reakcióidőkre, a megfelelő szelektivitásra és a minél jobb kihozatalokra. munkánk során kihasználtuk a mikrohullámú (MW) reakciómegvalósítás és a fázistranszfer katalízis adta lehetőséget, és ahol lehetett ott oldószer alkalmazása nélkül viteleztük ki a reakciókat. A vizsgált reakciók közül a foszfinsavak észteresítése, átészteresítések, C-alkilezések, a Pudovik-reakció, a Kabachnik–Fields kondenzáció, az Arbuzov-reakció és a Hirao-reakció a legfontosabbak. Fontos törekvésünk volt bizonyos katalizátorok helyettesítése MW besugárzással, ill. katalizátor-rendszerek egyszerűsítése MW körülmények között. Elméleti számításokkal tisztáztuk néhány általunk vizsgált reakció energetikáját és magyaráztuk a MW jótékony hatását. A foszfin-oxidok reszolválásával, majd azt követő deoxigénezésével platina-komplexekben hasznosítható optikailag aktív P-ligandumokhoz jutottunk. A Pt-komplexeket hidroformilezésekben teszteltük katalizátorként. Munkánk eredményeként lehetőség nyílik egy sereg – a gyógyszeripar ill. a finomkémiai ipar szempontjából fontos – foszfor-kémiai reakció környezetbarátabb megvalósítására és felesleges katalizátorok elhagyására, azok egyszerűsítésére, ill. az általunk kifejlesztett katalizátorok alkalmazására.
Results in English
In the course of our research, environmentally-friendly methods were applied during the realization of organophosphorus reactions. Atomic efficiency, the elimination and replacement of harmful and expensive reagents, catalysts and solvents, shorter reaction times, selectivity and high yields were the main objectives. We tried to utilize the possibilities offered by the microwave (MW) technique and phase transfer catalysis. Where it was possible, the reactions were performed under solvent-free conditions. From among the chemical transformations studied, the esterification of phosphinic acids, transesterifications, C-alkylations, the Pudovik reaction, the Kabachnik–Fields condensation, the Arbuzov reaction and the Hirao reaction were the most important. Furthermore, we wished to substitute certain catalysts by MW irradiation, and we tried to simplify catalytic systems under MW conditions. The energetics of a few reactions investigated were evaluated by quantum chemical calculations, and the beneficial effect of the MWs was explained. Optical resolution of the phosphine oxides followed by deoxygenation led to P-ligands useful in platinum complexes that were tested as catalysts in the hydroformylation of styrene. As a result of our work, environmentally-friendly accomplishment of a number of organophosphorus transformations that are important from the point of view pharmaceutical and fine chemical industry became possible.
Full text https://www.otka-palyazat.hu/download.php?type=zarobeszamolo&projektid=83118
Decision
Yes





 

List of publications

  
Keglevich G, Bagi P, Szöllősy Á, Körtvélyesi T, Pongrácz P, Kollár L, Drahos L: Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholenes and 1-propyl-phospholane P-ligands [...], J Organomet Chem 696: 3557-3563, 2011
Keglevich G, Grün A, Molnár IG, Greiner I: Phenyl-, benzyl- and unsymmetrical hydroxy-methylenebisphosphonates as dronic acid ester analogues from alpha-oxophosphonates by microwave-assisted synthesis, Heteroatom Chem 22: 640-648, 2011
Pietrusiewicz KM, Flis A, Ujj V, Körtvélyesi T, Drahos L, Pongrácz P, Kollár L, Keglevich G: Synthesis and use of borane- and platinum(II) complexes of 3-diphenylphosphino-1-phenylphospholane (LuPhos), Heteroatom Chem 22: 730-736, 2011
Kiss NZ, Kaszás A, Drahos L, Mucsi Z, Keglevich G: A neighbouring group effect leading to enhanced nucleophilic substitution of amines at the hindered alpha-carbon atom of an alpha-hydroxyphosphonate, Tetrahedron Lett 53: 207-209, 2012
Jablonkai E, Bálint E, Balogh GT, Drahos L, Keglevich G: Cyclic phosphinates by the alkylation of a thermally unstable 1-hydroxy-1,2-dihydrophosphinine 1-oxide and a 3-hydroxy-3-phosphabicyclo[310]hexane 3-oxide, Phosphorus, Sulfur, Silicon 187: 357-363, 2012
Keglevich G, Kiss NZ, Mucsi Z, Körtvélyesi T: Insights into a surprising reaction: The microwave-assisted direct esterification of phosphinic acids, Org Biomol Chem 10: 2011-2018, 2012
Bálint E, Fazekas E, Pintér G, Szöllősy Á, Holczbauer T, Czugler M, Drahos L, Körtvélyesi T, Keglevich G: Synthesis and utilization of the bis(>P(O)CH2)amine derivatives obtained by the double Kabachnik–Fields reaction with cyclohexylamine; Quantum chemical and X-ray [...], Current Org Chem 16: 547-554, 2012
Keglevich G, Kiss NZ, Menyhárd D, Fehérvári A, Csontos I: A study on the Kabachnik–Fields reaction of benzaldehyde, cyclohexylamine and dialkyl phosphites, Heteroatom Chem 23: 171-178, 2012
Bálint E, Takács J, Drahos L, Keglevich G: Microwave-assisted phospha-Michael addition of dialkyl phosphites, a phenyl-H-phosphinate, and diphenylphosphine oxide to maleic derivatives, Heteroatom Chem 23: 235-240, 2012
Grün A, Blastik Z, Drahos L, Keglevich G: Microwave-assisted alkylation of diethyl ethoxycarbonylmethylphosphonate under solventless conditions, Heteroatom Chem 23: 241-246, 2012
Bálint E, Fazekas E, Pongrácz P, Kollár L, Drahos L, Holczbauer T, Czugler M, Keglevich G: N-benzyl and N-aryl bis(phospha-Mannich adducts): Synthesis and catalytic activity of the related bidentate chelate platinum complexes in hydroformylation, J Organomet Chem 717: 75-82, 2012
Jablonkai E, Drahos L, Drzazga Z, Koprowski M, Pietrusiewicz KM, Keglevich G: 3-P(O)< Functionalized phospholane 1-oxides by the Michael reaction of 1-phenyl-2-phospholene 1-oxide and dialkyl phosphites, H-phosphinates or diphenylphosphine oxide, Heteroatom Chem 23: 539-544, 2012
Kiss NZ, Böttger É, Drahos L, Keglevich G: Microwave-assisted direct esterification of cyclic phosphinic acids, Heteroatom Chem (közlésre elfogadva), 2013
Keglevich G, Kiss NZ, Drahos L, Körtvélyesi T: Direct esterification of phosphinic acids under microwave conditions; extension to the synthesis of thiophosphinates and new mechanistic insights, Tetrahedron Lett 54: 466-469, 2013
Keglevich G, Kiss NZ, Körtvélyesi T: Microwave-assisted functionalization of phosphinic acids; Amidations versus esterifications, Heteroatom Chem 24: 91-99, 2013
Keglevich G, Kiss NZ, Körtvélyesi T, Mucsi Z: Direct esterification and amidation of phosphinic acids under microwave conditions, Phosphorus, Sulfur, Silicon 188: 29-32, 2013
Kiss NZ, Simon A, Drahos L, Huben K, Jankovski S, Keglevich G: Synthesis of 1-amino-2,5-dihydro-1H-phosphole 1-oxides and their N-phosphinoyl derivatives, bis(2,5-dihydro-1H-phoshol-1-yl)amine P,P'-dioxides, Synthesis 45: 199-204, 2013
Bálint E, Tajti Á, Drahos L, Ilia G, Keglevich G: Alcoholysis of dialkyl phosphites under microwave conditions, Current Org Chem 17: 555-562, 2013
Keglevich G, Grün A, Bölcskei A, Drahos L, Kraszni M, Balogh GT: Synthesis and proton dissociation properties of arylphosphonates; A microwave-assisted catalytic Arbuzov reaction with aryl bromides, Heteroatom Chem 23: 574-582, 2012
Bálint E, Fazekas E, Takács J, Tajti Á, Juranovič A, Kočevar M, Keglevich G: Microwave-assisted synthesis of organophosphorus compounds, Phosphorus, Sulfur, Silicon 188: 48-50, 2013
Bálint E, Takács J, Drahos L, Juranovič A, Kočevar M, Keglevich G: alpha-Aminophosphonates and alpha-aminophosphine oxides by the microwave-assisted Kabachnik–Fields reactions of 3-amino-6-methyl-2H-pyran-2-ones, Heteroatom Chem 24: 221-225, 2013
Keglevich G, Kovács R, Jablonkai E, Grün A, Greiner I: Environmentally friendly syntheses and tools, Phosphorus, Sulfur, Silicon 188: 39-41, 2013
Keglevich G, Grün A, Bálint E, Kiss NZ, Jablonkai E: Microwave-assisted organophosphorus synthesis, Current Org Chem 17: 545-554, 2013
Keglevich G, Greiner I: The meeting of two disciplines: organophosphorus and green chemistry, Current Green Chem (közlésre elfogadva), 2013
Keglevich G: The potential of microwave in organophosphorus syntheses, Bentham Science Newsletter 4: 1-4, 2012
Keglevich Gy: Munkára fogott mikrohullámok, Élet és Tudomány 22: 691-693, 2013
Keglevich G, Kiss NZs, Bálint E, Kovács R, Jablonkai E, Fazekas E, Tóth J, Kaszás A, Blastik Z, Grün A: Synthesis of organophosphorus compounds under microwave conditions, Vol 37, pp 1350-1353 in: 5th Eur. Conf. of the Int. Federat. for Medical and Biolog. Eng. (IFMBE), Budapest, 2011 szept 14-18, Ed: Jobbágy A, IFMBE Proceedings, Budapest, 2012
Grün A, Milen M, Földesi T, Ábrányi-Balogh P, Drahos L, Keglevich G: Microvawe-assisted amidation of arylacetic acids by reaction with 2-aryl-ethylamines, Synthetic Commun 43: 1491-1498, 2013
Bálint E, Kovács O, Drahos L, Keglevich G: Microwave-assisted solid–liquid phase alkylation of naphthols, Lett Org Chem 10: 330-336, 2013
Keglevich G, Grün A, Bálint E: Microwave irradiation and phase transfer catalysis in C-, O- and N-alkylation reactions, Current Org Synth (közlésre elfogadva), 2013
Milen M, Ábrányi-Balogh P, Balogh G, Drahos L, Keglevich G: A study on the phosphorylation of indole, imidazole, carbazole and phenothiazine derivatives, Phosphorus, Sulfur, Silicon 187: 1091-1100, 2012
Keglevich G, Bálint E: The Kabachnik–Fields reaction; mechanism and synthetic use, Molecules 17: 12821-12835, 2012
Bagi P, Laki A, Keglevich G: Preparation of optically active six-membered P-heterocycles a 3-phosphabicyclo[310]hexane 3-oxide, a 1,2-dihydrophosphinine 1-oxide, and a 1,2,3,6-tetrahydro[...], Heteroatom Chem 24: 179-186, 2013
Bagi P, Kovács T, Szilvási T, Pongrácz P, Kollár L, Drahos L, Fogassy E, Keglevich G: Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholene P-ligands; Synthesis, stereostructure, NMR properties and catalytic activity, J Organomet Chem (közlésre elfogadva), 2013
Bagi P, Kovács T, Laki A, Fekete A, Fogassy E, Keglevich G: Resolution of 5- and 6-membered p-heterocycles; racemic and optically active platinum(II)-3-phospholene complexes, Phosphorus, Sulfur, Silicon 188: 36-38, 2013
Kovács R, Balogh G T, Ludányi K, Drahos L, Keglevich G: A study on the reduction of 4-chloro-1,2-dihydrophosphinine oxides by transfer hydrogenation, Phosphorus, Sulfur, Silicon 187: 121-127, 2012
Keglevich G, Grün A, Kovács R, Koós K, Szolnoki B, Garadnay S, Neu J, Drahos L, Greiner I: Heteroarylacetyl chlorides and mixed anhydrides as intermediates in the synthesis of heterocyclic dronic acids, Lett Drug Des Discov 9: 345-351, 2012
Keglevich G, Bagi P Bálint E, Körtvélyesi T: The synthesis of platinum complexes of cyclic phosphines and bisphosphines, pp 83-102 in: Varennikov L, Yedemsky E. Platinum Compounds, Production and Applications. Nova Science Publishers Inc, New York, 2013
Keglevich G, Bálint E, Kiss NZ, Jablonkai E, Hegedűs L, Grün A, Greiner I: Microwave-assisted esterification of phosphinic acids, Current Org Chem 15: 1802-1810, 2011
Keglevich G, Bagi P, Szöllősy Á, Körtvélyesi T, Pongrácz P, Kollár L, Drahos L: Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholenes and 1-propyl-phospholane P-ligands [...], J Organomet Chem 696: 3557-3563, 2011
Keglevich G, Grün A, Molnár IG, Greiner I: Phenyl-, benzyl- and unsymmetrical hydroxy-methylenebisphosphonates as dronic acid ester analogues from alpha-oxophosphonates by microwave-assisted synthesis, Heteroatom Chem 22: 640-648, 2011
Pietrusiewicz KM, Flis A, Ujj V, Körtvélyesi T, Drahos L, Pongrácz P, Kollár L, Keglevich G: Synthesis and use of borane- and platinum(II) complexes of 3-diphenylphosphino-1-phenylphospholane (LuPhos), Heteroatom Chem 22: 730-736, 2011
Kiss NZ, Kaszás A, Drahos L, Mucsi Z, Keglevich G: A neighbouring group effect leading to enhanced nucleophilic substitution of amines at the hindered alpha-carbon atom of an alpha-hydroxyphosphonate, Tetrahedron Lett 53: 207-209, 2012
Jablonkai E, Bálint E, Balogh GT, Drahos L, Keglevich G: Cyclic phosphinates by the alkylation of a thermally unstable 1-hydroxy-1,2-dihydrophosphinine 1-oxide and a 3-hydroxy-3-phosphabicyclo[310]hexane 3-oxide, Phosphorus, Sulfur, Silicon 187: 357-363, 2012
Keglevich G, Kiss NZ, Mucsi Z, Körtvélyesi T: Insights into a surprising reaction: The microwave-assisted direct esterification of phosphinic acids, Org Biomol Chem 10: 2011-2018, 2012
Bálint E, Fazekas E, Pintér G, Szöllősy Á, Holczbauer T, Czugler M, Drahos L, Körtvélyesi T, Keglevich G: Synthesis and utilization of the bis(>P(O)CH2)amine derivatives obtained by the double Kabachnik–Fields reaction with cyclohexylamine; Quantum chemical and X-ray [...], Current Org Chem 16: 547-554, 2012
Keglevich G, Kiss NZ, Menyhárd D, Fehérvári A, Csontos I: A study on the Kabachnik–Fields reaction of benzaldehyde, cyclohexylamine and dialkyl phosphites, Heteroatom Chem 23: 171-178, 2012
Bálint E, Takács J, Drahos L, Keglevich G: Microwave-assisted phospha-Michael addition of dialkyl phosphites, a phenyl-H-phosphinate, and diphenylphosphine oxide to maleic derivatives, Heteroatom Chem 23: 235-240, 2012
Grün A, Blastik Z, Drahos L, Keglevich G: Microwave-assisted alkylation of diethyl ethoxycarbonylmethylphosphonate under solventless conditions, Heteroatom Chem 23: 241-246, 2012
Kiss NZ, Böttger É, Drahos L, Keglevich G: Microwave-assisted direct esterification of cyclic phosphinic acids, Heteroatom Chem 24:283-288, 2013
Bálint E, Takács J, Drahos L, Juranovič A, Kočevar M, Keglevich G: alpha-Aminophosphonates and alpha-aminophosphine oxides by the microwave-assisted Kabachnik–Fields reactions of 3-amino-6-methyl-2H-pyran-2-ones, Heteroatom Chem 24: 221-225, 2013
Keglevich G, Greiner I: The meeting of two disciplines: organophosphorus and green chemistry, Current Green Chem 1: 2-16, 2014
Keglevich G: The potential of microwave in organophosphorus syntheses, Bentham Science Newsletter 4: 1-4, 2012
Keglevich G, Kiss NZs, Bálint E, Kovács R, Jablonkai E, Fazekas E, Tóth J, Kaszás A, Blastik Z, Grün A: Synthesis of organophosphorus compounds under microwave conditions, Vol 37, pp 1350-1353 in: 5th Eur. Conf. of the Int. Federat. for Medical and Biolog. Eng. (IFMBE), Budapest, 2011 szept 14-18, Ed: Jobbágy A, IFMBE Proceedings, Budapest, 2012
Grün A, Milen M, Földesi T, Ábrányi-Balogh P, Drahos L, Keglevich G: Microvawe-assisted amidation of arylacetic acids by reaction with 2-aryl-ethylamines, Synthetic Commun 43: 1491-1498, 2013
Keglevich G, Grün A, Bálint E: Microwave irradiation and phase transfer catalysis in C-, O- and N-alkylation reactions, Current Org Synth 10: 751-763, 2013
Milen M, Ábrányi-Balogh P, Balogh G, Drahos L, Keglevich G: A study on the phosphorylation of indole, imidazole, carbazole and phenothiazine derivatives, Phosphorus, Sulfur, Silicon 187: 1091-1100, 2012
Bagi P, Kovács T, Szilvási T, Pongrácz P, Kollár L, Drahos L, Fogassy E, Keglevich G: Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholene P-ligands; Synthesis, stereostructure, NMR properties and catalytic activity, J Organomet Chem 751: 306-313, 2014
Kovács R, Balogh G T, Ludányi K, Drahos L, Keglevich G: A study on the reduction of 4-chloro-1,2-dihydrophosphinine oxides by transfer hydrogenation, Phosphorus, Sulfur, Silicon 187: 121-127, 2012
Keglevich G, Grün A, Kovács R, Koós K, Szolnoki B, Garadnay S, Neu J, Drahos L, Greiner I: Heteroarylacetyl chlorides and mixed anhydrides as intermediates in the synthesis of heterocyclic dronic acids, Lett Drug Des Discov 9: 345-351, 2012
Jablonkai E, Keglevich G: P-ligand-free, microwave-assisted variation of the Hirao reaction under solvent-free conditions; the P–C coupling reaction of >P(O)H species and bromoarenes, Tetrahedron Lett 54: 4185-4188, 2013
Milen M, Ábrányi-Balogh P, Dancsó A, Frigyes D, Pongó L, Keglevich G: T3P®-promoted Kabachnik–Fields reaction: an efficient synthesis of α-aminophosphonates, Tetrahedron Lett 54, 5430-5433, 2013
Jablonkai E, Milen M, Drahos L, Keglevich G: Esterification of five-membered cyclic phosphinic acids under mild conditions using propylphosphonic anhydride (T3P®), Tetrahedron Lett 54, 5873-5875, 2013
Bálint E, Fazekas E, Drahos L, Keglevich G: The synthesis of N,N-bis(dialkoxyphosphinoylmethyl)- and N,N-bis(diphenylphosphinoylmethyl) glycine esters by the microwave-assisted double Kabachnik–Fields reaction, Heteroatom Chem 24: 510-515, 2013
Bálint E, Kállai M, Kovács O, Bölcskei H, Keglevich G: O-Arylation of iodophenols with 2-fluorobenzaldehyde under microwave conditions, Lett Drug Des Discov 11: 114-120, 2014
Bagi P, Kállay M, Hessz D, Kubinyi M, Holczbauer T, Czugler M, Fogassy E, Keglevich G: Resolution of 1-n-propoxy-3-methyl-3-phospholene 1-oxide by diastereomeric complex formation using TADDOL derivatives and calcium salts of O,O’-dibenzoyl-(2R,3R)- [...], Tetrahedron Asym 25: 318-326, 2014
Grün A, Blastik Z, Drahos L, Keglevich G: Dialkylation of diethyl ethoxycarbonylmethylphosphonate under microwave and solventless conditions, Heteroatom Chem 25: 107-113, 2014
Keglevich G, Kovács T: Silanes as reagents for the deoxygenation of tertiary phosphine oxides – A case study for the deoxygenation of 5-membered cyclic phosphine oxides, Current Green Chem 1: 182-188, 2014
Grün A, Kovács R, Nagy DI, Garadnay S, Greiner I, Keglevich G: The rational synthesis of Fenidronate, Lett Org Chem 11: 368-373, 2014
Keglevich G, Kiss NZ, Mucsi Z, Jablonkai E, Bálint E: The synthesis of phosphinates: traditional versus green chemical approaches, Green Process Synth 3: 103-110, 2014
Kovács R, Grün A, Garadnay S, Greiner I, Keglevich G: “Greener” synthesis of bisphosphonic/dronic acid derivatives, Green Process Synth 3: 111-116, 2014
Keglevich G, Bálint E, Takács J, Drahos L, Huben K, Jankowski S: The addition of dialkyl phosphites and diphenylphosphine oxide on the triple bond of dimethyl acetylenedicarboxylate under solvent-free and microwave conditions, Current Org Synth 11: 161-166, 2014
Mucsi Z, Kiss NZ, Keglevich G: A quantum chemical study on the mechanism and energetics of the direct esterification, thioesterification and amidation of 1-hydroxy-3-methyl-3-phospholene 1-oxide, RSC Adv 4: 11948-11954, 2014
Kovács R, Grün A, Németh O, Garadnay S, Greiner I, Keglevich G: The synthesis of pamidronic derivatives in different solvents: an optimization and a mechanistic study, Heteroatom Chem 25: 186-193, 2014
Jablonkai E, Keglevich G: P–C bond formation by coupling reaction utilizing >P(O)H species as the reagents, Current Org Synth 11: 429-453, 2014
Hägele G, Dettmann J, Huben K, Jankowski S, Bálint E, Keglevich G: 1,2-bisphosphonosuccinic acid hexamethylester [(CH3O)2(O)P-CH-COOCH3]2 - NMR-spectroscopic studies of ABX and [AM3R3X]2+Z6 systems, Phosphorus, Sulfur, Silicon (közlésre elfogadva), 2014
Bagi P, Fekete A, Kállay M, Hessz D, Kubinyi M, Holczbauer T, Czugler M, Fogassy E, Keglevich G: Resolution of 1-n-butyl-3-methyl-3-phospholene 1-oxide with TADDOL derivatives and calcium salts of O,O’-dibenzoyl-(2R,3R)- or O,O’-di-p-toluoyl-(2R,3R)-tartaric acid, Chirality (közlésre elfogadva), 2014
Kiss NZ, Mucsi Z, Böttger É, Drahos L, Keglevich G: A three-step conversion of phenyl-1H-phosphinic acid to dialkyl phenylphosphonates including two microwave-assisted direct esterification steps, Current Org Synth (közlésre elfogadva), 2014
Keglevich G: Microwave-assisted synthesis of P-heterocycles, Phosphorus, Sulfur, Silicon (közlésre elfogadva), 2014
Milen M, Ábrányi-Balogh P, Kangyal R, Dancsó A, Frigyes D, Keglevich G: T3P®-mediated one-pot synthesis of bis(α-aminophosphonates), Heteroatom Chem (közlésre elfogadva), 2014
Keglevich G, Jablonkai E, Balázs L B: A “green” variation of the Hirao reaction: the P–C coupling of diethyl phosphite, alkyl phenyl-H-phosphinates and secondary phosphine oxides with bromoarenes [...], RSC Adv 4: 22808-22816, 2014
Jablonkai E, Keglevich G: Advances and new variations of the Hirao reaction, Org Prep Proc Int (közlésre elfogadva), 2014
Kiss NZ, Örkényi R, Mucsi Z, Keglevich G: The synthesis of 3-phosphabicyclo[3.1.0]hexane 3-oxides and 1,2-dihydrophosphinine 1-oxides with lipophilic P-alkoxy substituents by ring enlargement, Heteroatom Chem (közlésre elfogadva), 2014
Bagi P, Szilvási T, Pongrácz P, Kollár L, Drahos L, Keglevich G: Platinum(II) complexes incorporating racemic and optically active 1-aryl-3-phospholene P-ligands; Synthesis, stereostructure, NMR properties and catalytic activity, Current Org Chem (közlésre elfogadva), 2014
Keglevich G, Bálint E, Kangyal R, Bálint M, Milen M: A critical overview of the Kabachnik–Fields reactions utilizing trialkyl phosphites in water as the reaction medium; A study on the benzaldehyde [...], Heteroatom Chem (közlésre elfogadva), 2014
Keglevich G, Grün A, Bagi P, Bálint E, Kiss NZ, Kovács R, Jablonkai E, Kovács T, Fogassy E, Greiner I: Environmentally friendly chemistry with organophosphorus syntheses in the focus, Per Politechn Chem Eng (közlésre elfogadva), 2014
Keglevich G: Application of microwave irradiation in the synthesis of P-heterocycles, Springer, (közlésre elfogadva), 2014
Kiss NZ, Böttger É, Drahos L, Keglevich G: Microwave-assisted direct esterification of cyclic phosphinic acids, Heteroatom Chem 24:283-288, 2013
Keglevich G, Kiss NZ, Drahos L, Körtvélyesi T: Direct esterification of phosphinic acids under microwave conditions; extension to the synthesis of thiophosphinates and new mechanistic insights, Tetrahedron Lett 54: 466-469, 2013
Keglevich G, Kiss NZ, Körtvélyesi T: Microwave-assisted functionalization of phosphinic acids; Amidations versus esterifications, Heteroatom Chem 24: 91-99, 2013
Keglevich G, Kiss NZ, Körtvélyesi T, Mucsi Z: Direct esterification and amidation of phosphinic acids under microwave conditions, Phosphorus, Sulfur, Silicon 188: 29-32, 2013
Kiss NZ, Simon A, Drahos L, Huben K, Jankovski S, Keglevich G: Synthesis of 1-amino-2,5-dihydro-1H-phosphole 1-oxides and their N-phosphinoyl derivatives, bis(2,5-dihydro-1H-phoshol-1-yl)amine P,P'-dioxides, Synthesis 45: 199-204, 2013
Bálint E, Tajti Á, Drahos L, Ilia G, Keglevich G: Alcoholysis of dialkyl phosphites under microwave conditions, Current Org Chem 17: 555-562, 2013
Bálint E, Fazekas E, Takács J, Tajti Á, Juranovič A, Kočevar M, Keglevich G: Microwave-assisted synthesis of organophosphorus compounds, Phosphorus, Sulfur, Silicon 188: 48-50, 2013
Bálint E, Takács J, Drahos L, Juranovič A, Kočevar M, Keglevich G: alpha-Aminophosphonates and alpha-aminophosphine oxides by the microwave-assisted Kabachnik–Fields reactions of 3-amino-6-methyl-2H-pyran-2-ones, Heteroatom Chem 24: 221-225, 2013
Keglevich G, Kovács R, Jablonkai E, Grün A, Greiner I: Environmentally friendly syntheses and tools, Phosphorus, Sulfur, Silicon 188: 39-41, 2013
Keglevich G, Grün A, Bálint E, Kiss NZ, Jablonkai E: Microwave-assisted organophosphorus synthesis, Current Org Chem 17: 545-554, 2013
Grün A, Milen M, Földesi T, Ábrányi-Balogh P, Drahos L, Keglevich G: Microvawe-assisted amidation of arylacetic acids by reaction with 2-aryl-ethylamines, Synthetic Commun 43: 1491-1498, 2013
Bálint E, Kovács O, Drahos L, Keglevich G: Microwave-assisted solid–liquid phase alkylation of naphthols, Lett Org Chem 10: 330-336, 2013
Keglevich G, Grün A, Bálint E: Microwave irradiation and phase transfer catalysis in C-, O- and N-alkylation reactions, Current Org Synth 10: 751-763, 2013
Bagi P, Laki A, Keglevich G: Preparation of optically active six-membered P-heterocycles a 3-phosphabicyclo[310]hexane 3-oxide, a 1,2-dihydrophosphinine 1-oxide, and a 1,2,3,6-tetrahydro[...], Heteroatom Chem 24: 179-186, 2013
Bagi P, Kovács T, Szilvási T, Pongrácz P, Kollár L, Drahos L, Fogassy E, Keglevich G: Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholene P-ligands; Synthesis, stereostructure, NMR properties and catalytic activity, J Organomet Chem 751: 306-313, 2014
Bagi P, Kovács T, Laki A, Fekete A, Fogassy E, Keglevich G: Resolution of 5- and 6-membered p-heterocycles; racemic and optically active platinum(II)-3-phospholene complexes, Phosphorus, Sulfur, Silicon 188: 36-38, 2013
Keglevich G, Bagi P Bálint E, Körtvélyesi T: The synthesis of platinum complexes of cyclic phosphines and bisphosphines, pp. 83-102 in: Varennikov L, Yedemsky E. Platinum Compounds, Production and Applications. Nova Science Publishers Inc, New York, 2013
Jablonkai E, Keglevich G: P-ligand-free, microwave-assisted variation of the Hirao reaction under solvent-free conditions; the P–C coupling reaction of >P(O)H species and bromoarenes, Tetrahedron Lett 54: 4185-4188, 2013
Milen M, Ábrányi-Balogh P, Dancsó A, Frigyes D, Pongó L, Keglevich G: T3P®-promoted Kabachnik–Fields reaction: an efficient synthesis of α-aminophosphonates, Tetrahedron Lett 54, 5430-5433, 2013
Jablonkai E, Milen M, Drahos L, Keglevich G: Esterification of five-membered cyclic phosphinic acids under mild conditions using propylphosphonic anhydride (T3P®), Tetrahedron Lett 54, 5873-5875, 2013
Bálint E, Fazekas E, Drahos L, Keglevich G: The synthesis of N,N-bis(dialkoxyphosphinoylmethyl)- and N,N-bis(diphenylphosphinoylmethyl) glycine esters by the microwave-assisted double Kabachnik–Fields reaction, Heteroatom Chem 24: 510-515, 2013
Bálint E, Kállai M, Kovács O, Bölcskei H, Keglevich G: O-Arylation of iodophenols with 2-fluorobenzaldehyde under microwave conditions, Lett Drug Des Discov 11: 114-120, 2014
Bagi P, Kállay M, Hessz D, Kubinyi M, Holczbauer T, Czugler M, Fogassy E, Keglevich G: Resolution of 1-n-propoxy-3-methyl-3-phospholene 1-oxide by diastereomeric complex formation using TADDOL derivatives and calcium salts of O,O’-dibenzoyl-(2R,3R)- [...], Tetrahedron Asym 25: 318-326, 2014
Grün A, Blastik Z, Drahos L, Keglevich G: Dialkylation of diethyl ethoxycarbonylmethylphosphonate under microwave and solventless conditions, Heteroatom Chem 25: 107-113, 2014
Grün A, Kovács R, Nagy DI, Garadnay S, Greiner I, Keglevich G: The rational synthesis of Fenidronate, Lett Org Chem 11: 368-373, 2014
Keglevich G, Bálint E, Takács J, Drahos L, Huben K, Jankowski S: The addition of dialkyl phosphites and diphenylphosphine oxide on the triple bond of dimethyl acetylenedicarboxylate under solvent-free and microwave conditions, Current Org Synth 11: 161-166, 2014
Mucsi Z, Kiss NZ, Keglevich G: A quantum chemical study on the mechanism and energetics of the direct esterification, thioesterification and amidation of 1-hydroxy-3-methyl-3-phospholene 1-oxide, RSC Adv 4: 11948-11954, 2014
Kovács R, Grün A, Németh O, Garadnay S, Greiner I, Keglevich G: The synthesis of pamidronic derivatives in different solvents: an optimization and a mechanistic study, Heteroatom Chem 25: 186-193, 2014
Jablonkai E, Keglevich G: P–C bond formation by coupling reaction utilizing >P(O)H species as the reagents, Current Org Synth 11: 429-453, 2014
Hägele G, Dettmann J, Huben K, Jankowski S, Bálint E, Keglevich G: 1,2-bisphosphonosuccinic acid hexamethylester [(CH3O)2(O)P-CH-COOCH3]2 - NMR-spectroscopic studies of ABX and [AM3R3X]2+Z6 systems, Phosphorus, Sulfur, Silicon 189: 1315-1327, 2014
Bagi P, Fekete A, Kállay M, Hessz D, Kubinyi M, Holczbauer T, Czugler M, Fogassy E, Keglevich G: Resolution of 1-n-butyl-3-methyl-3-phospholene 1-oxide with TADDOL derivatives and calcium salts of O,O’-dibenzoyl-(2R,3R)- or O,O’-di-p-toluoyl-(2R,3R)-tartaric acid, Chirality 26: 174-182, 2014
Kiss NZ, Mucsi Z, Böttger É, Drahos L, Keglevich G: A three-step conversion of phenyl-1H-phosphinic acid to dialkyl phenylphosphonates including two microwave-assisted direct esterification steps, Current Org Synth 11:767-772, 2014
Keglevich G: Microwave-assisted synthesis of P-heterocycles, Phosphorus, Sulfur, Silicon 189: 1266-1278, 2014
Milen M, Ábrányi-Balogh P, Kangyal R, Dancsó A, Frigyes D, Keglevich G: T3P®-mediated one-pot synthesis of bis(α-aminophosphonates), Heteroatom Chem 22: 245-255, 2014
Keglevich G, Jablonkai E, Balázs L B: A “green” variation of the Hirao reaction: the P–C coupling of diethyl phosphite, alkyl phenyl-H-phosphinates and secondary phosphine oxides with bromoarenes [...], RSC Adv 4: 22808-22816, 2014
Jablonkai E, Keglevich G: Advances and new variations of the Hirao reaction, Org Prep Proc Int 46: 281-316, 2014
Kiss NZ, Örkényi R, Mucsi Z, Keglevich G: The synthesis of 3-phosphabicyclo[3.1.0]hexane 3-oxides and 1,2-dihydrophosphinine 1-oxides with lipophilic P-alkoxy substituents by ring enlargement, Heteroatom Chem 25: 265-273, 2014
Bagi P, Szilvási T, Pongrácz P, Kollár L, Drahos L, Keglevich G: Platinum(II) complexes incorporating racemic and optically active 1-aryl-3-phospholene P-ligands as potential catalysts in hydroformylation, Current Org Chem 18: 1529-1538, 2014
Keglevich G, Bálint E, Kangyal R, Bálint M, Milen M: A critical overview of the Kabachnik–Fields reactions utilizing trialkyl phosphites in water as the reaction medium; A study on the benzaldehyde [...], Heteroatom Chem 25: 282-289, 2014
Keglevich G, Grün A, Bagi P, Bálint E, Kiss NZ, Kovács R, Jablonkai E, Kovács T, Fogassy E, Greiner I: Environmentally friendly chemistry with organophosphorus syntheses in the focus, Per Polytechn Chem Eng 59: 82-95, 2015
Keglevich G: Application of microwave irradiation in the synthesis of P-heterocycles, Ch. 20, pp. 559-570 in: Brahmachari G. Green Synthetic Approaches for Biologically Relevant Heterocycles. Elsevier, Amsterdam, 2015
Kiss NZ, Keglevich G: An overview of the synthesis of phosphinates and phosphinic amides, Current Org. Chem. 18, 2673-2690, 2014
Keglevich G, Kiss NZ, Mucsi Z: Synthesis of phosphinic acid derivatives; Traditional versus up-to-date synthetic procedures, Chem. Sci. J. 5: 1000088 (2014). doi: 10.4172/2150-3494.1000088, 2014
Keglevich G, Bálint E, Tajti Á, Mátravölgyi B, Balogh GT, Bálint M, Ilia G: Microwave-assisted alcoholysis of dialkyl phosphites by ethylene glycol and ethanolamine, Pure Appl Chem 86: 1723-1728, 2014
Grün A, Kovács R, Nagy DI, Garadnay S, Greiner I, Keglevich G: Effective synthesis of benzidronate applying of phosphorus trichloride and phosphorous acid, Lett Drug Des Discov 12: 78-84, 2015
Grün A, Kovács R, Garadnay S, Greiner I, Keglevich G: The synthesis of Risedronic acid and Alendronate applying phosphorus oxychloride and phosphorous acid in methanesulfonic acid, Lett Drug Des Discov 12: 253-258, 2015
Bagi P, Fekete A, Kállay M, Hessz D, Kubinyi M, Holczbauer T, Czugler M, Fogassy E, Keglevich G: A case-study on the resolution of the 1-i-butyl-3-methyl-3-phospholene 1-oxide via diastereomeric complex formation using TADDOL derivatives and via diastereomeric coordination complexes formed [...], Heteroatom Chem 26: 79-90, 2015
Bálint E, Fazekas E, Mucsi Z, Kóti J, Keglevich G: Synthesis of N,N-bis(dialkoxyphosphinoylmethyl)- and N,N-bis(diphenylphosphinoylmethyl)-β- and γ-amino acid derivatives by the microwave-assisted double Kabachnik–Fields reaction, Heteroatom Chem 26: 106-115, 2015
Jablonkai E, Keglevich G: Catalyst-free P-C coupling reaction of halobenzoic acids and secondary phosphine oxides under microwave irradiation in water, Tetrahedron Lett 56: 1638-1640, 2015
Jablonkai E, Balázs LB, Keglevich G: A P-ligand-free nickel-catalyzed variation of the Hirao reaction under microwave conditions, Current Org Chem 19: 197-202, 2015
Jablonkai E, Henyecz R, Milen M, Kóti J, Drahos L, Keglevich G: T3P®-assisted esterification and amidation of phosphinic acids, Tetrahedron 70: 8280-8285, 2014
Kiss NZ, Rádai Z, Mucsi Z, Keglevich G: Synthesis of bis(phosphinoyl)amines and phosphinoyl-phosphorylamines by the N-phosphinoylation and N-phosphorylation of 1-alkylamino-2,5-dihydro-1H-phosphole 1-oxides, Heteroatom Chem 26: 134-141, 2015
Grün A, Bálint E, Keglevich G: Solid–liquid phase C-alkylation of active methylene containing compounds under microwave conditions, Catalysts 5: 634-652, 2015
Keglevich G, Greiner I, Mucsi Z: An interpretation of the rate enhancing effect of microwaves – modelling the distribution and effect of local overheating – A case study, Current Org Chem 19: 1436-1440, 2015
Keglevich G, Kiss NZ, Jablonkai E, Bálint E, Mucsi Z: The potential of microwave in organophosphorus syntheses, Phosphorus, Sulfur, Silicon 190: 647-654, 2015
Bálint E, Fazekas E, Tripolszky A, Kangyal R, Milen M, Keglevich G: Synthesis of α-aminophosphonate derivatives by microwave-assisted Kabachnik–Fields reaction, Phosphorus, Sulfur, Silicon 190: 655-659, 2015
Jablonkai E, Balázs LB, Keglevich G: MW-Assisted P–C coupling reaction using P-ligand-free Pd(OAc)2 catalyst, Phosphorus, Sulfur, Silicon 190: 660-663, 2015
Keglevich G, Grün A, Kovács R, Garadnay S, Greiner I: Green chemical synthesis of bisphosphonic/dronic acid derivatives, Phosphorus, Sulfur, Silicon 190: 664-667, 2015
Kiss NZ, Mucsi Z, Rádai Z, Böttger É, Keglevich G: The synthesis and potential use of cyclic phosphinic acid derivatives, Phosphorus, Sulfur, Silicon 190: 668-671, 2015
Bagi P, Kovács T, Kollár L, Fogassy E, Keglevich G: Novel platinum(II) – complexes incorporating optically active P-heterocycles as the ligands, Phosphorus, Sulfur, Silicon 190: 821-823, 2015
Bagi P, Juhász K, Timári I, E Kövér K, Mester D, Kállay M, Kubinyi M, Szilvási T, Pongrácz P, Kollár L, Karaghiosoff K, Czugler M, Drahos L, Fogassy E, Keglevich G: A study on the optical resolution of 1-isopropyl-3-methyl-3-phospholene 1-oxide and its use in the synthesis of borane and platinum complexes, J Organomet Chem 797: 140-152, 2015
Bagi P, Ujj V, Czugler M, Fogassy E, Keglevich G: Resolution of P-stereogenic P-heterocycles via the formation of diastereomeric molecular and coordination complexes, Dalton Trans 45: 1823-1842, 2016
Keglevich G, Grün A: Microwave irradiation as a substitute for phase transfer catalyst in C-alkylation reactions, Current Green Chem 2: 254-263, 2015
Keglevich G: Microwave in organophosphorus syntheses, Trends in Green Chem 1: 1-6 (2015) http://green-chemistryimedpubcom/archivephp, 2015
Kovács T, Fülöp L Sz, Mucsi Z, Karaghiosoff K, Czugler M, Keglevich G: Revisiting the 7-phospanorbornene family; New P-alkyl derivatives, Heteroatom Chem 26: 335-347, 2015
Bálint E, Takács J, Bálint M, Keglevich G: The catalyst-free addition of dialkyl phosphites on the triple bond of alkyl phenylpropiolates under microwave conditions, Current Cat 4: 57-64, 2015
Jablonkai E, Keglevich G: A survey of the palladium–catalyzed Hirao reaction with emphasis on green chemical aspects, Current Green Chem 2: 379-391, 2015
Keglevich G, Grün A, Garadnay S, Greiner I: Rational synthesis of dronic acid derivatives, Phosphorus, Sulfur, Silicon 190: 2116-2124, 2015
Bálint E, Tripolszky A, Jablonkai E, Karaghiosoff K, Czugler M, Mucsi Z, Kollár L, Pongrácz P, Keglevich G: Synthesis and use of α-aminophosphine oxides and N,N-bis(phosphinoyl-methyl)amines – A study on the related ring platinum complexes, J Organomet Chem 801: 111-121, 2015
Kovács T, Urbanics A, Csatlós F, Binder J, Falk A, Uhlig F, Keglevich G: A study on the deoxygenation of phosphine oxides by different silane derivatives, Current Org Synth 13: 148-153, 2016
Grün A, Nagy DI, Garadnay S, Greiner I, Keglevich G: Efficient synthesis of pamidronic acid using an ionic liquid additive, Lett Drug Des Discov (in press), 2016
Jablonkai E, Keglevich G: P–C Coupling reactions under environmentally-friendly conditions, Vol. 10, pp. 99-125 in: VM Petrova. Advances in Engineering Research. Nova Science Publishers Inc, New York, 2015
Kovács T, Fülöp LSz, Keglevich G: Fragmentation-related phosphonylation of nucleophiles utilizing P-alkyl 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide precursors, Heteroatom Chem (in press), 2016
Keglevich G, Bálint E, Kiss NZ, Jablonkai E, Hegedűs L, Grün A, Greiner I: Microwave-assisted esterification of phosphinic acids, Current Org Chem 15: 1802-1810, 2011



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