The synthesis and use of phosporus heterocycles  Page description

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Details of project

  
Identifier
42479
Type K
Principal investigator Keglevich, György
Title in Hungarian Foszforheterociklusok szintézise és hasznosítása
Title in English The synthesis and use of phosporus heterocycles
Panel Chemistry 2
Department or equivalent Department of Organic Chemistry and Technology (Budapest University of Technology and Economics)
Participants Balázsdi Szabó, Nóra
Bat Amgalan, Namkhainyambuu
Farkas, Renáta
Forintos, Henrietta
Hegedűs, László
Imre, Tímea
Jankowski, Stefan
Körtvélyesi, Tamás
Kovács, János
Ludányi, Krisztina
Novák, Tibor
Odinets, Irina Leonovna
Polonkáné Bálint, Ágnes
Sipos, Melinda
Szelke, Helga
Szöllősy, Áron
Vékey, Károly
Vinogradova, Natalya Mikchailovna
Starting date 2003-01-01
Closing date 2007-12-31
Funding (in million HUF) 22.966
FTE (full time equivalent) 0.00
state closed project





 

Final report

  
Results in Hungarian
A kutatás három fő szálon futott, egyrészt az 5- és 6-tagú, másrészt a 7- és 8-tagú – ez utóbbi esetben áthidalt – P-heterociklusok területén, harmadrészt egy inverz Wittig-típusú reakció témájában. Újfajta foszfol- és a 3-as helyzetben foszforfunkciót tartalmazó 1,2,3,6-tetra- és 1,2,3,4,5,6-hexahidrofoszfinin P-ligandokat (ill. ez utóbbiak prekurzorait) tettük hozzáférhetővé, amelyeket átmeneti fémkomplexekké is átalakítottunk. A P-ligandok és a komplexek térszerkezetét felderítettük és ez utóbbiak egy részét katalizátorként is kipróbáltuk. Jónéhány dibenzooxafoszforint – közöttük optikai aktivitással rendelkező származékokat is – előállítottunk. A ligandok platina-komplexeit is elkészítettük. A kutatás másik vonalán új 7-foszfanorbornén, ill. 2-foszfabiciklo[2.2.2]oktén 2-oxid származékokat vezettünk be, egyrészt új szubsztituensek, másrészt új dienofilek alkalmazásával. A prekurzorokat reakcióképes intermedierek képzésén át foszforilezési reakciókban hasznosítottuk. Tanulmányoztuk a reakciók mechanizmusát és oxafoszfabiciklookténeket is vizsgáltunk. A harmadik témában a P-aril gyűrűs foszfin-oxidok és a dialkilacetiléndikarboxilát béta-oxofoszforánokat eredményező reakcióinak mechanizmusát derítettük fel és megfontoltuk az oxafoszfetének mint intermedierek lehetőségét. A béta-oxofoszforánokat kerülő szintézissel is hozzáférhetővé tettük és tanulmányoztuk néhány jellemző reakciójukat.
Results in English
The research was performed in three topics, on one hand in the topic of 5- and 6-membered P-heterocycles, on the other hand in the field of 7- and 8-membered P-cycles including bridged derivatives, and finally in the topic of the inverse Wittig type reaction. New phosphole and 1,2,3,6-tetra- and 1,2,3,4,5,6-hexahydrophosphinine P-ligands – these latter with exocyclic P-function in position three – were made available that were also transformed to transition metal complexes. Stereostructure of the P-ligands and complexes was evaluated and a part of the latter was tested as catalyst. A number of dibenzooxaphosphorines and their platinum complexes were also prepared. In the second line of the research, new 7-phosphanorbornene- and 2-phosphabicyclo[2.2.2]octene 2-oxide derivatives were introduced and utilized in fragmentation related phosphorylation of nucleophiles. Beside the mechanistic studies, oxaphosphabicyclooctenes were also studied. In the third topic, the mechanism of the inverse Wittig type reaction of cyclic phosphine oxides and dialkyl acetylenedicarboxylate resulting in beta-oxophosphoranes was studied. Oxaphosphetes were considered as possible intermediates. The beta-oxophosphoranes were also prepared by an independent synthesis and some of their reactions were investigated.
Full text http://real.mtak.hu/620/
Decision
Yes





 

List of publications

  
Keglevich Gy, Kovács J, Szelke H, Körtvélyesi T: A study on the ability of 2,5-dihydro- and 2,3,4,5-tetrahydro-1H-phosphole oxides, as well as 7-phosphanorbornene 7-oxide derivatives to undergo UV light-mediated fragmentation-related phosphinylation of methanol., J. Heterocyclic Chem. 43: 723, 2006
Keglevich Gy, Forintos H, Körtvélyesi T: Synthesis and reactions of beta-oxophosphoranes/ylides containing a cyclic or acyclic P-moiety., Current Org. Chem. 8: 1245, 2004
Keglevich Gy, Forintos H, Ujvári A, Imre T, Ludányi K, Nagy Z, Tőke L: Reactions of beta-oxo-alfa,beta-bis(alkoxycarbonyl)phosphonium ylides based on P-heterocycles., J. Chem. Res. 432, 2004
Keglevich Gy, Sipos M, Lengyel D, Forintos H, Körtvélyesi T, Imre T, Tőke L: Synthesis of 1-aryl-1,2,3,4,5,6-hexahydrophosphinine 1-oxides., Synth. Commun. 34: 4159, 2004
Kovács J, Keglevich Gy, Kerényi A, Imre T, Ludányi K, Tőke L: The reaction of dichlorocarbene with phosphine derivatives related on the 2-methyl-1-phenyl-2,5-dihydro and 2,3,4,5-tetrahydro-1H-phosphole moiety., Heterocyclic Commun. 10: 283, 2004
Keglevich Gy, Kégl T, Odinets IL, Vinogradova NM, Kollár L: Carbonylation reactions catalysed by rhodium(III) and palladium(II) complexes containing novel phosphine ligands., Compt. Rend. Chimie, 7: 779, 2004
Keglevich Gy, Sipos M, Szieberth D, Nyulászi L, Imre T, Ludányi K, Tőke L: Weak intramolecular interactions as controlling factors in the diastereoselective formation of 3-phosphinoxido- and 3-phosphono-1,2,3,6-tetrahydrophosphinine 1-oxides., Tetrahedron 6619, 2004
Keglevich Gy, Szelke H, Kovács J: Fragmentation-related phosphinylation and phosphonylation of nucleophiles utilising the bridging P-unit of 2-phosphabicyclo[2.2.2]oct-5-ene derivatives., Current Org. Synth. 1: 377, 2004
Kovács J, Imre T, Ludányi K, Tőke L, Keglevich Gy: Efficient synthesis of 2,8-diphosphatricyclo[5.3.1.12,6]dodeca-3,5,9-triene 2,8-dioxides., Synth. Commun. 34: 1033, 2004
Keglevich Gy, Sipos M, Szieberth D, Petőcz Gy, Kollár L: 4-Chloro-5-methyl-3-diphenylphosphino-1-phenyl-1,2,3,6-tetrahydrophosphinine as a bidentate P-ligand in a cis chelate Pt(II) complex., J. Organomet. Chem. 689: 3158, 2004
Szelke H, Ludányi K, Imre T, Nagy Z, Vékey K, Tőke L, Keglevich Gy: Efficient synthesis of mixed phosphonates by the fragmentation-related phosphorylation of alcohols applying a 2-phosphabicyclo[2.2.2]octa-5,7-diene 2-oxide precursor., Synth. Commun. 34: 4171, 2004
Keglevich Gy, Kovács J, Körtvélyesi T, Parlagh Gy, Imre T, Ludányi K, Hegedűs L, Hanusz M, Simon K, Márton A, Marosi Gy, Tőke L: Novel 2-phosphabicyclo[2.2.2]oct-5-ene derivatives and their use in phosphinylations., Heteroatom Chem. 15: 97, 2004
Keglevich Gy, Forintos H, Szelke H, Kovács J, Körtvélyesi T: [4+2] vs [2+2] cikloaddíciók a foszforheterociklusok körében., Magy. Kém. Folyóirat 109/110: 37, 2004
Jankowski S, Keglevich Gy, Nonas T, Forintos H, Glowka M, Rudzinski J: Aryl-2,3-oxaphosphabicyclo[2.2.2]octene derivatives - the precursors of oxoarylphosphine oxides (aryl metaphosphonates)., Tetrahedron 60: 2789, 2004
Keglevich Gy, Farkas R, Ludányi K, Kudar V, Hanusz M, Simon K: New P-ligands; the aromaticity and reactivity of 2,4,6-trialkylphenylphospholes., Heteroatom Chem. 16: 104, 2005
Keglevich Gy, Sipos M, Körtvélyesi T, Imre T, Tőke L: 1,2,3,4,5,6-Hexahydrophosphinine 1-oxides with an exocyclic P-function at position 3: Diastereoselective synthesis, stereostructure and conformation., Tetrahedron Lett. 46: 1655, 2005
Körtvélyesi T, Sipos M, Keglevich Gy: A theoretical study on the conformation of 3-phosphinoxido- and 3-phosphono-1,2,3,4,5,6-hexahydrophosphinine 1-oxides., Heteroatom Chem. 16: 520, 2005
Keglevich Gy, Sipos M, Ujj V, Körtvélyesi T: Synthesis of 3-phosphinoxido- and 3-phosphono-1,2,3,4,5,6-hexahydrophosphinine oxides as potential precursors of bidentate P-ligands., Letters in Org. Chem. 2: 608, 2005
Odinets IL, Vinogradova NM, Lyssenko KA, Golovanov DG, Petrovskii PV, Mastryukova TA, Szelke H, Balázsdi Szabó N, Keglevich Gy: Rhodium(III) and palladium(II) complexes of some P-heterocycles; synthesis and X-ray structures., J. Organomet. Chem. 690: 704, 2005
Odinets IL, Vinogradova NM, Matveeva EV, Golovanov DD, Lyssenko KA, Keglevich Gy, Kollár L, Roeschenthaler GV, Mastryukova TA: Novel functionalised P-ligands: advances and application., J. Organomet. Chem. 690: 2559, 2005
Keglevich Gy: Exciting fields in P-heterocyclic chemistry., J. Heterocyclic Chem. 42: 451, 2005
Szelke H, Bálint Á, Király E, Ludányi K, Kovács J, Keglevich Gy: 2-Ethyl-2-phosphabicyclo[2.2.2]oct-7-ene derivatives; Synthesis and use in fragmentation-related phosphorylations., Heteroatom Chem. 16: 196, 2005
Kovács J, Balázsdi Szabó N, Nagy Z, Ludányi K, Keglevich Gy: New 7-phosphanorbornenes derived from 2-methyl-1-phenyl- and 1-cyclohexyl-3-methyl-2,5-dihydro-1H-phosphole 1-oxides., Heteroatom Chem. 16: 320, 2005
Szelke H, Kovács J, Keglevich Gy: Synthesis of H-phosphinates by the UV light–mediated fragmentation-related phosphorylation using simple P-heterocycles., Synth. Commun. 35: 2927, 2005
Keglevich Gy, Forintos H, Ujvári A, Ludányi K, Bitter I, Tőke L: Generation and utilisation of P-cyclic alpha-methoxycarbonyl-methylenephosphoranes., J. Chem. Res. 215, 2005
Keglevich Gy, Szelke H, Kerényi A, Kudar V, Hanusz M, Simon K, Imre T, Ludányi K: New chiral P-ligands: P-amino- and P-cycloalkoxy dibenzo[c.e][1,2]oxaphosphorines., Tetrahedron Asym. 16: 4015, 2005
Keglevich Gy, Körtvélyesi T, Ujvári A, Dudás E: A quantum chemical study on the reaction of 1-aryl-1,2-dihydrophosphinine oxides with dimethyl acetylenedicarboxylate., J. Organomet. Chem. 690: 2497, 2005
Odinets I, Kégl T, Sharova E, Artyushin O, Goryunov E, Molchanova G, Lyssenko K, Mastryukova T, Röschenthaler GV, Keglevich Gy, Kollár L: Novel alpha-fluorinated cyclic phosphite and phosphinite ligands and their Rh-complexes as suitable catalyts in hydroformylation., J. Organomet. Chem. 690: 3456, 2005
Keglevich Gy: Synthesis and reactivity of 1-(2,4,6-trialkylphenyl)phospholes having a flattened P-pyramid., Vol. 6, pp. 245-269 in: Attanasi, OA, Spinelli D. Eds. Targets in Heterocyclic Systems. Italian Society of Chemistry, 2003
Keglevich Gy, Farkas R, Imre T, Ludányi K, Szöllősy Á, Tőke L: 2,4,6-Trialkylphenyl-2H-phospholes from slightly aromatic 1H-phospholes and their use in [4+2] cycloaddition reactions., Heteroatom Chem. 14: 316, 2003
Keglevich Gy, Kégl T, Chuluunbaatar T, Dajka B, Mátyus P, Balogh B, Kollár L: Hydroformylation of styrene in the presence of rhodium-2,4,6-trialkylphenyl-phosphole in situ catalytic systems., J. Mol. Catal. 200: 131, 2003
Odinets I, Körtvélyesi T, Kégl T, Kollár L, Keglevich Gy: Rh complexes of 1-(2,4,6-triisopropylphenyl-)3-methyl-1H-phosphole; Preparation and use as catalysts in the hydroformylation of styrene., Transit Metal Chem. in press, 2007
Keglevich Gy: 6-Membered P-heterocycles: 1,2-Dihydro-, 1,2,3,6-tetrahydro- and 1,2,3,4,5,6-hexahydrophosphinine 1-oxides., Current Org. Chem. 10: 93, 2006
Keglevich Gy, Szelke H, Kerényi A, Imre T: Bis(dibenzo[c.e][1,2]oxaphosphorino-)dichloroplatinum complexes., Transit Metal Chem. 31: 306, 2006
Keglevich Gy, Kerényi A, Szelke H, Ludányi K, Körtvélyesi T: Diphenylphosphino-2’-hydroxybiphenyl-based P-ligands and their platinum(II) complexes., J. Organomet. Chem. 691: 5038, 2006
Novák T, Schindler J, Ujj V, Czugler M, Fogassy E, Keglevich Gy: Resolution of 3-methyl-3-phospholene 1-oxides by molecular complex formation with TADDOL derivatives., Tetrahedron Asym. 17: 2599, 2006
Frank É, Körtvélyesi T, Czugler M, Keglevich Gy: New steroid-fused P-heterocycles. Part I.: Synthesis and conformational study of dioxaphosphorino[16,17-d]estrone derivatives., Steroids in press, 2007
Frank É, Kazi B, Mucsi Z, Ludányi K, Keglevich Gy: New steroid-fused P-heterocycles. Part II.: Synthesis and conformational study of oxazaphosphorino[16,17-e]estrone derivatives., Steroids in press, 2007
Frank É, Schäfer B, Mucsi Z, Keglevich Gy: Synthesis and conformational study of P-heterocyclic androst-5-ene derivatives., Heteroatom Chem. in press, 2007
Artyushin O, Odinets I, Goryunov E, Goryunova I, Fedyanin I, Lyssenko K, Mastryukova T, Röschenthaler GV, Kégl T, Keglevich Gy, Kollár L: Alfa-Fluorinated cyclic amidophosphite ligands. Their synthesis, Rh complexes and catalytic activity in the hydroformylation of styrene., J. Organomet. Chem. 691: 5547, 2006
Keglevich Gy, Szelke H, Bálint Á, Imre T, Ludányi K, Nagy Z, Hanusz M, Simon K, Harmat V, Tőke L: Fragmentation-related phosphinylations using 2-aryl-2-phosphabicyclo[2.2.2]oct-5-ene- and -octa-5,7-diene-2-oxides., Heteroatom Chem. 14: 443, 2003
Jankowski S, Kovács J, Huben K, Blaszczyk M, G³ówka M, Keglevich Gy: Regioselective formation of a 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide in Baeyer-Villiger type oxidation; a dual pathway for its fragmentation., Heteroatom Chem. 17: 369, 2006
Keglevich Gy, Dudás E, Sipos M, Lengyel D, Ludányi K: Efficient synthesis of cyclic beta-oxophosphoranes by the microwave-assisted reaction of cyclic phosphine oxides and dialkyl acetylenedicarboxylate., Synthesis, 1365, 2006
Mucsi Z, Körtvélyesi T, Viskolcz B, Csizmadia IG, Novák T, Keglevich Gy: Can four member heterophosphete structures exist? “Heterogen” hetero antiaromaticity as a destabilizing effect., Eur. J. Org. Chem. in press, 2007
Keglevich Gy, Baán Z, Hermecz I, Novák T, Odinets IL: The phosphorus aspects of green chemistry: the use of quaternary phosphonium salts and 1,3-dialkylimidazolium hexafluorophosphates in organic synthesis., Current. Org. Chem. in press, 2007
Keglevich Gy, Dudás E: Microwave promoted efficient synthesis of 2-phosphabicyclo[2.2.2]octadiene- and octene 2-oxides under solventless conditions in Diels-Alder reaction., Synth. Commun. in press, 2007



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