Homogeneous asymmetric carbonylation reactions and their mechanistic investigations  Page description

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Details of project

 
Identifier
113177
Type K
Principal investigator Kollár, László
Title in Hungarian Homogénkatalitikus aszimmetrikus karbonilezési reakciók és mechanizmus-vizsgálatuk
Title in English Homogeneous asymmetric carbonylation reactions and their mechanistic investigations
Keywords in Hungarian szén-monoxid, átmenetifém, palládium, platina, enantioszelektivitás
Keywords in English carbon monoxide, transition metal, palladium, platinum, enantioselectivity
Discipline
Inorganic Chemistry (Council of Physical Sciences)60 %
Ortelius classification: Organometallic Chemistry
Organic, Biomolecular, and Pharmaceutical Chemistry (Council of Physical Sciences)40 %
Ortelius classification: Intermedier chemistry
Panel Elnöki zsüri
Department or equivalent Department of Inorganic Chemistry (University of Pécs)
Participants Kégl, Tamás
Nagymihály, Zoltán
Pongrácz, Péter
Takács, Attila
Starting date 2015-01-01
Closing date 2019-12-31
Funding (in million HUF) 24.809
FTE (full time equivalent) 11.27
state running project





 

Final report

 
Results in Hungarian
A karbonilezési (szén-monoxid építőelem beépülésével járó) reakciók az iparban leggyakrabban alkalmazott homogénkatalitikus eljárások közé tartoznak. A projekt keretében – a legszélesebb körben ismert hidroformilezési reakción túl – foglalkoztunk alkének átmenetifém-katalizált hidroalkoxi/hidroariloxikarbonilezési reakcióival, valamint aril- és alkenil-halogenidek alkoxikarbonilezési és aminokarbonilezési reakcióival. Ily módon különböző észterek és karbonsavamidok állíthatók elő nagy kemo-, regio- és enantioszelektiivtással. A fenti reakciók között kitüntetett jelentőségűek a királis terméket eredményezők; ezekben az esetekben enantioszelektív/diasztereoszelektív átalakításokat valósítottunk meg. Pályázatunkban e reakciók mechanizmusának feltárásával, a katalitikus reakció elemi lépéseinek, valamint a szerkezet-reaktivitás és szerkezet-szelektivitás összefüggések vizsgálatával foglalkoztunk, konkrét aszimmetrikus és normál szintézisek egész sorát megvalósítva.
Results in English
The carbonylation reactions (using carbon monoxide as C1 building block) belong to one of the most extensively applied homogeneous catalytic processes in industry. In the framework of this project, in addition to the well-known hydroformylation reaction, hydroalkoxycarbonylation /hydroaryloxycarbonylation of alkenes, as well as alkoxycarbonylation/aryloxycarbonylation/aminocarbonylation of aryl and alkenyl halides were carried out. In this way, esters and carboxamides of various structures can be synthesised in chemo-, regio- and enantioselective manner. Among the above reactions, priviliged ones are those resulting in chiral product(s). In these cases, transition metal-catalysed enantio- and diastereoselective reactions were carried out. The mechanistic details of the various carbonylations and their elementary steps were investigated. Furthermore, the structure-reactivity and structure-selectivity relations were studied with several specific examples.
Full text https://www.otka-palyazat.hu/download.php?type=zarobeszamolo&projektid=113177
Decision
Yes





 

List of publications

 
P. Bagi, K. Juhász, I. Timári, K. Kövér, M. Kállay, D. Mester, M. Kubinyi, T. Szilvási, P. Pongrácz, L. Kollár, K. Karaghiosoff, M. Czugler, L. Drahos, E. Fogassy, G. Keglevich:: The resolution of 1-i-propyl-3-methyl-3-phospholene-oxide and its use as a precursor for a P-ligand., J. Organomet. Chem. 797 (2015) 140-152., 2015
E. Bálint, A. Tripolszky, E. Jablonkai, Z. Mucsi, P. Pongrácz, L. Kollár, G. Keglevich:: Synthesis and use of N,N-bis(phosphinoylmethyl)amines – A study on the related ring platinum complexes., J. Organomet. Chem. 801 (2016) 111-121., 2016
P. Pongrácz, L. Kollár, L. Mika: A step towards hydroformylation under green conditions: platinum-catalysed enantioselective hydroformylation of styrene in gamma-valerolactone., Green Chem. 000 (2016) 000-000. ( DOI: 10.1039/C5GC01778E), 2016
T.R. Kégl, L. Kollár, T. Kégl: DFT Study on the Oxidative Addition of 4-Substituted Iodobenzenes on Pd(0)-Phosphine Complexes., Adv. Phys. Chem. Volume 2015, Article ID 985268, (http://dx.doi.org/10.1155/2015/985268), 2015
A. Takács, D. Marosvölgyi-Haskó, Z. Kabak-Solt, L. Damas, F.M.S. Rodrigues, R.M.B. Carrilho, M. Pineiro, M.M. Pereira, L. Kollár: Functionalization of Indole at C-5 or C-7 via Palladium-Catalysed Double Carbonylation. A Facile Synthesis of Indole Ketocarboxamides and Carboxamide Dimers., Tetrahedron 72 (2016) 247-256., 2016
G. Szőke, A. Takács, L. Kollár: Synthesis of Pyridazine Carboxamides via Palladium-Catalysed Aminocarbonylation., J. Heterocycl. Chem. 000 (2016) 000-000. (DOI: 10.1002/jhet.2523), 2016
R. Farkas, A. Petz, L. Kollár: Synthesis of 2-(1,4-dioxaspiro[4,5]decan-6yl)acrylamides from 2-Acetylcyclohexanone via Palladium-catalysed Aminocarbonylation., Monatsh. Chem. 146 (2015) 1665-1671., 2015
E. Szánti-Pintér, J. Wouters, Á. Gömöry, É. Sághy, É. Szőke, Z. Helyes, L. Kollár, R. Skoda-Földes: Synthesis of Novel 13α-18-Norandrostane-ferrocene Conjugates via Homogeneous Catalytic Methods and their Investigation on TRPV1 Receptor Activation., Steroids 104 (2015) 284-293., 2015
M. Kiss, S. Mahó, K. Böddi, B. Boros, L. Kollár: Palladium-Catalyzed Diaminocarbonylation. Synthesis of Androstene Dimers Containing 3,3’- or 17,17’-Dicarboxamide Spacers., Monatsh. Chem. 146 (2015) 357-364., 2015
T. Z. Jánosi, G. Makkai, T. R. Kégl, P. Mátyus, L. Kollár, J. Erostyák: Light-enhanced fluorescence of multi-level cavitands possessing pyridazine upper rim., J. Fluorescence 000 (2016) 000-000 (DOI: 10.1007/s10895-015-1754-3), 2016
Z. Csók, P. Szuroczki, L. Kollár, H. M. Ngo, I. Ledoux-Rak, N. A. M. S. Caturelles, R. Q. Albuquerque: Intramolecular Cooperative effects in Multichromophoric Cavitands Exhibiting Nonlinear Optical Properties., J. Phys. Chem. C. 119 (2015) 12608-12615., 2015
Z. Nagymihály, L. Kollár: High-yielding Synthesis of Deepened Cavitands Bearing Picolyl Moieties on the Upper Rim., Tetrahedron 71 (2015) 2555-2560., 2015
M. Kiss, A. Takács, L. Kollár: Highly selective synthesis of carboxamides via transition metal catalysed aminocarbonylation., Curr. Green Chem. 2 (2015) 319-338., 2015
P. Pongrácz, L. Kollár, L. Mika: A step towards hydroformylation under green conditions: platinum-catalysed enantioselective hydroformylation of styrene in gamma-valerolactone., Green Chem. 18 (2016) 842-847., 2016
G. Szőke, A. Takács, L. Kollár: Synthesis of Pyridazine Carboxamides via Palladium-Catalysed Aminocarbonylation., J. Heterocycl. Chem. 53 (2016) 2020-2024., 2016
T. Z. Jánosi, G. Makkai, T. R. Kégl, P. Mátyus, L. Kollár, J. Erostyák: Light-enhanced fluorescence of multi-level cavitands possessing pyridazine upper rim., J. Fluorescence 26 (2016) 582-588., 2016
P. Pongrácz, L. Kollár:: Enantioselective Hydroformylation of 2- and 4-Substituted Styrenes with PtCl2[(R)-BINAP] + SnCl2 ‘in situ’ Catalyst: a Substituent Effect on the Reversal of Enantioselect, J. Organomet. Chem., 2016
P. Bagi, K. Karaghiosoff, M. Czugler, D. Hessz, M. Kállay, M. Kubinyi, T. Szilvási, P. Pongrácz, L. Kollár, I. Timári, K. E. Kövér, L. Drahos, E. Fogassy, G. Keglevich:: Synthesis, Characterization and Application of Platinum(II) Complexes Incorporating Racemic and Optically Active 1-Phenyl-1,2,3,6-Tetrahydrophosphinine Ligand., Heteroatom Chem. 27 (2016) 91-101., 2016
D. Marosvölgyi-Haskó, B. Lengyel, J. M. Tukacs,, L. Kollár, L. Mika:: Application of -valerolactone as an alternative biomass-based medium for aminocarbonylation reactions., ChemPlusChem 81 (2016) 1224–1229., 2016
D. Marosvölgyi-Haskó, T. Kégl, L. Kollár:: Aminocarbonylation of para-substituted iodobenzenes. Substituents effect for mono-and double carbonylation., Tetrahedron 72 (2016) 7509-7516., 2016
G. Mikle, B. Boros, L. Kollár:: Synthesis of Bornene – 2,2’-Diamino-1,1’-binaphthalene Conjugates in Palladium-Catalysed Aminocarbonylation., Tetrahedron: Asymm. 27 (2016) 377-383., 2016
G. Szőke, A. Takács, Z. Berente, A. Petz and L. Kollár:: Synthesis of Amino-substituted Pyridylglyoxylamides via Palladium-Catalysed Aminocarbonylation., Tetrahedron 72 (2016) 3063-3067., 2016
M. Gergely, A. Takács , L. Kollár:: 4-Amino-TEMPO as N-Nucleophile in Palladium-Catalysed Aminocarbonylation., J. Heterocyclic Chem., 2017
M. Gergely, L. Kollár:: Aminocarbonylation (Hydrazinocarbonylation) of Iodoalkenes and Iodoarenes.., Tetrahedron, 2017
P. Pongrácz, L. Kollár:: Asymmetric Hydroformylation of 4-Vinyl-1,3-dioxolan-2-one., J. Heterocyclic Chem., 2017
Z. Czibulya, É. Horváth, Z. Nagymihály, L. Kollár, S. Kunsági-Máté:: Competitive processes associated to the interaction of a cavitand derivative with caffeic acid., Supramol. Chem. 28 (2016) 582-588., 2016
G. Secenji, G. Matisz, Z. Csók, L. Kollár, S. Kunsági-Máté:: Temperature-dependent quenching of fluorescence of a cavitand derivative with copper ions., Chem. Phys. Lett. 657 (2016) 60-64., 2016
Z. Nagymihály, N. A. M. S. Caturello, A. Takátsy, L. Kollár, R. Q. Albuquerque, Z. Csók:: Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-Sorting on a Cavitand Platform, J. Org. Chem., 2017
M. Gergely, A. Takács , L. Kollár:: 4-Amino-TEMPO as N-Nucleophile in Palladium-Catalysed Aminocarbonylation., J. Heterocyclic Chem. 54 (2017) 634-640., 2017
M. Gergely, L. Kollár:: Aminocarbonylation (Hydrazinocarbonylation) of Iodoalkenes and Iodoarenes.., Tetrahedron 73 (2017) 838-844., 2017
P. Pongrácz, L. Kollár:: Asymmetric Hydroformylation of 4-Vinyl-1,3-dioxolan-2-one., J. Heterocyclic Chem. 54 (2017) 1430-1436., 2017
A. Takács, G. M. Varga, J. Kardos, L. Kollár:: Palladium-catalysed aminocarbonylation of diiodopyridines., Tetrahedron 73 (2017) 2131-2138., 2017
Z. Nagymihály, N. A. M.S.Caturello, A. Takátsy, L. Kolár, R. Q. Albuquerque, Z. Csók:: Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-sorting on a Cavitand Platform., J. Org. Chem. 82 (2017) 390-396., 2017
P. Pongrácz, B. Bartal, L. Kollár, L. Mika:: Rh-catalyzed hydroformylation in gamma-valerolactone as a biomass-based reaction medium., J. Organomet. Chem. 847 (2017) 140-145., 2017
P. Pongrácz, A. Abu Seni, L. T. Mika, L. Kollár:: Palladium-catalysed Enantioselective Hydroaryloxycarbonylation of Styrenes by 4-Substituted Phenols., Mol. Catal. 428 (2017) 15-18., 2017
P. Pongrácz, H. Szentjóbi, T. Tóth, P. Huszthy, L. Kollár:: Platinum(II)–monophospha-crown ether complexes: their coordination chemistry and hydroformylation activity., Mol. Catal. 439 (2017) 128-133., 2017
T. Papp, L. Kollár, T. Kégl:: Theoretical Insights into the Nature of Pt-Sn Bond. Reevaluating the Coordinating Properties of Trichlorostannate., J. Comput. Chem. 38 (2017) 1712-1726., 2017
N. Pálinkás, L. Kollár, T. Kégl:: Nature of the Metal-Ligand Interactions in Complexes M(PH3)2(eta-2-L) (M=Ni, Pd, Pt; L=CO2, COS, CS2): A theoretical Study., Chem. Select 2 (2017) 5740-5750., 2017
N. Pálinkás, L. Kollár, T. Kégl:: Viable pathways for the oxidative addition of iodobenzene to palladium(0)-triphenylphosphine-carbonyl complexes: a theoretical study., Dalton Trans. 46 (2017) 15789-15802., 2017
M. Gergely, B: Boros, L. Kollár:: High-yielding synthesis of N-triazolyl carboxamides via palladium-catalysed aminocarbonylation., Tetrahedron 73 (2017) 6736-6741., 2017
E. Szánti-Pintér, L. Maksó, Á. Gömöry, J. Wouters, B. E. Herman, M. Szécsi, L. Kollár, R. Skoda-Földes:: Synthesis of 16α-Amino-pregnenolone Derivatives via Ionic Liquid-catalyzed aza-Michael Addition and their Evaluation as C17,20-Lyase Inhibitors., Steroids 123 (2017) 61-66., 2017
T. Kégl, G. Csekő, G. Mikle, A. Takátsy, T. Kégl, L. Kollár:: Investigation of weak interactions among the cavitand branches of novel triazole ring containing compounds., Chem. Select 2 (2017) 8337-8345., 2017
G. Mikle, B. Boros, L. Kollár:: Asymmetric Aminocarbonylation of Iodoalkenes in the Presence of -Phenylethylamine as N-Nucleophile., Tetrahedron: Asymm. 28 (2017) 1733-1738., 2017
L. Kollár, P. Pongrácz: Tandem hydroformylation/aldol condensation reactions: synthesis of unsaturated ketones from olefins., J. Organomet. Chem. 866 (2018) 184-188., 2018
N. Pálinkás, L. Kollár, T. Kégl: Palladium-Catalysed Synthesis of Amidines via Isonitrile Insertion., ACS Omega 3 (2018) 16118−16126, 2018
Z. Nagymihály, Z. Csók, L. Kollár: Influence of base additives on the selectivity of palladium-catalysed aminocarbonylation: highly selective functionalization of a cavitand scaffold., Mol. Catal. 44 (2018) 780-785, 2018
B. Urbán; P. Szabó; D. Srankó, Gy. Sáfrán, L. Kollár; R. Skoda-Földes: Double carbonylation of iodoarenes in the presence of reusable palladium catalysts immobilised on supported phosphonium ionic liquid phases., Mol. Catal. 445 (2018) 195-205, 2018
K. Fehér, E. Nagy, P. Szabó, D. Srankó, Á. Gömöry, L. Kollár, R. Skoda-Földes: Heterogeneous azide-alkyne cycloaddition in the presence of a copper catalyst supported on an ionic liquid polymer/silica hybrid material., Appl. Organomet. Chem. 2018, DOI: 10.1002/aoc, 2018
L. Orha, J. M. Tukacs, B. Gyarmati, A. Szilágyi, L. Kollár, L. T. Mika: Modular Synthesis of gamma-Valerolactone-based Ionic Liquids and Their Application as Alternative Media for Copper-catalysed Ulmann-type Coupling reactions., ACS Sustainable Chem. & Engineering. 6 (2018) 5097-5104., 2018
A. Abu Seni, L, Kollár, L. T. Mika, P. Pongrácz: Rhodium-catalysed aryloxycarbonylation of iodo-aromatics by 4-substituted phenols with carbon monoxide or paraformaldehyde., Mol. Catal. 457 (2018) 67-73, 2018
M. Gergely, L. Kollár: Aminothiazoles and Aminothiadiazoles as Nucleophiles in Aminocarbonylation of Iodobenzene Derivatives., Tetrahedron 74 (2018) 2030-2040, 2018
A. Takács, L Kollár: Aminolactames as N-nucleophiles in aminocarbonylation reaction., Tetrahedron 74 (2018) 6116-6128, 2018
P. Szuroczki, B. Boros, L. Kollár: Efficient Synthesis of Alkynyl Amides via Aminocarbonylation of Iodoalkynes., Tetrahedron 74 (2018) 6129-6136, 2018
P. Szuroczki, G. Mikle, L. Kollár: Synthesis of oxazol derivatives from iodoalkenes via aminocarbonylation–cycloisomerization sequence in one-pot reaction., Mol. Catal. 452 (2018) 68-74, 2018
D. Ispán, E. Szánti-Pintér, M. Papp, J. Wouters, B. Zsirka, Á. Gömöry, L. Kollár, R. Skoda-Földes:: The use of switchable polarity solvents for the synthesis of 16-arylidene steroids via Claisen-Schmidt condensation., Eur. J. Org. Chem. (2018) 3236-3244, 2018
K. Fehér, E. Nagy, P. Szabó, D. Srankó, Á. Gömöry, L. Kollár, R. Skoda-Földes: Heterogeneous azide-alkyne cycloaddition in the presence of a copper catalyst supported on an ionic liquid polymer/silica hybrid material., Appl. Organomet. Chem. 2018, DOI: 10.1002/aoc, 2018
L. Orha, J. M. Tukacs, B. Gyarmati, A. Szilágyi, L. Kollár, L. T. Mika: Modular Synthesis of gamma-Valerolactone-based Ionic Liquids and Their Application as Alternative Media for Copper-catalysed Ulmann-type Coupling reactions., ACS Sustainable Chem. & Engineering. 6 (2018) 5097-5104., 2018
D. Ispán, E. Szánti-Pintér, M. Papp, J. Wouters, B. Zsirka, Á. Gömöry, L. Kollár, R. Skoda-Földes:: The use of switchable polarity solvents for the synthesis of 16-arylidene steroids via Claisen-Schmidt condensation., Eur. J. Org. Chem. (2018) 3236-3244, 2018
T. R. Kégl,, L. Kollár, T. Kégl:: Computational Characterization of Bidentate P-donor Ligands: Direct Comparision to Tolman’s Electronic Parameters., Molecules 23 (2018) 3176, 2018
B. Bartal, G. Mikle, L. Kollár, P. Pongrácz:: Palladium-catalysed carbonylations of alkyl and alkenyl halides with formic acid as carbonyl source. Synthesis of α,β-unsaturated carboxylic acids and esters., Mol. Catal. 467 (2019) 143−149., 2019
M. Gergely, L. Kollár:: Synthesis of Benzamide--Benzothiazole Conjugates via Palladium-Catalysed Aminocarbonylation (Hydrazinocarbonylation)., Tetrahedron 75 (2019) 2027−2036., 2019
P. Szuroczki, J. Sámson, L. Kollár:: Synthesis of 5-carboxamidotriazoles via azide-alkyne cycloaddition–aminocarbonylation sequence., ChemistrySelect 4 (2020) 5527-5530,, 2020
A. Takács, M. G. Varga, Á. Dörnyei, L. Kollár:: Functionalization of the Uracil Ring via Palladium-catalysed Aminocarbonylation., Tetrahedron 75 (2019) 4632-4639., 2019
A. Abu Seni, L. Kollár, P. Pongrácz:: Palladium-catalysed intramolecular asymmetric cyclohydroaryloxycarbonylation of 2-allylphenol derivatives. Synthesis of chiral lactones via cyclocarbonylation.., Mol. Catal. 482 (2020) 110673., 2020
P. Szuroczki, L. Molnár, Á. Dörnyei, L. Kollár:: Facile, high-yielding synthesis of 4-functionalised 1,2,3-triazoles via amino- and aryloxycarbonylation., ChemistrySelect (accepted), 2020
M. Gergely, A. Bényei, L. Kollár:: 2-Aminobenzimidazole and -benzoxazole as N-nucleophile in palladium-catalysed aminocarbonylation., Tetrahedron (accepted), 2020





 

Events of the project

 
2017-02-28 21:07:02
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