Search results for "katalyytit"
showing 10 items of 64 documents
Trans-(2,5)-disubstituoitujen pyrrolidiiniyhdisteiden enantioselektiivinen synteesi
2018
2,5-disubstituoitujen pyrrolidiinien enantioselektiivistä synteesiä on tutkittu paljon, sillä pyrrolidiinirakenne löytyy monista alkaloideista ja on täten tärkeä osa luonnonainesynteesiä. Lisäksi ne toimivat tärkeinä asymmetrisen synteesin työkaluina. Erityisen kiinnostavia tässä suhteessa ovat erilaiset trans-2,5-bisaryylipyrrolidiinit katalyyttisten ominaisuuksiensa vuoksi. Tässä tutkielmassa käydään läpi eräitä tapoja niiden syntetisoimiseksi. Tutkielmassa keskitytään erityisesti trans-2,5-difenyylipyrrolidiinin enantioselektiiviseen synteesiin.
Cu(ii)-thiophene-2,5-bis(amino-alcohol) mediated asymmetric Aldol reaction and Domino Knoevenagel Michael cyclization : a new highly efficient Lewis …
2022
The highly efficient Lewis acid-catalytic system Cu(II)-thiophene-2,5-bis(amino-alcohol) has been developed for enantioselective Aldol reaction of isatin derivatives with ketones. The new catalytic system also proved to be highly enantioselective for the one pot three-component Domino Knoevenagel Michael cyclization reaction of substituted isatin with malononitrile and ethylacetoacetate. The chiral ligand (2S,2′S)-2,2′-((thiophene-2,5-diylbis(methylene))bis(azanediyl))bis(3-phenylpropan-1-ol) (L1) in combination with Cu(OAc)2·H2O employed as a new Lewis acid catalyst, furnished 3-substituted-3-hydroxyindolin-2-ones derivatives (3a–s) in good to excellent yields (81–99%) with high enantiosel…
Fenyyli-ja metoksifenyylisubstituoidut karbokationit katalyytteinä
2018
Karbokationit ovat orgaanisia molekyylejä, joissa on positiivisesti varautunut hiiliatomi. Hybridisaatioteoria selittää karbokationien luonnetta ja kolmiulotteista rakennetta keskushiilen sp2-hybridisaatiolla, jossa hiiliatomin hybridisoitumaton p-orbitaali levittäytyy kolmen hybridiorbitaalin muodostaman tason ylä- ja alapuolille. Hybridisoitumaton porbitaali ei kuitenkaan ole täysin eristyksissä hybridisoituneista sidosorbitaaleista vaan se vastaanottaa helposti elektronitiheyttä keskushiileen sitoutuneilta substituenteilta. Mitä enemmän substituentit luovuttavat elektronitiheyttä positiivisesti varautuneelle hiiliatomille, sitä enemmän elektronitiheyttä siirtyy myös hybridisoitumattomall…
Iron(III) chloride as mild catalyst for the dearomatizing cyclization of N-acylindoles
2020
A catalytic approach for the preparation of indolines by dearomatizing cyclization is presented. FeCl3 acts as a catalyst to afford tetracyclic 5a,6-dihydro-12H-indolo[2,1-b][1,3]benzoxazin-12-ones in good yields. The cyclization also proceeds with tosylamides forming C-N bonds in 53 % yield. peerReviewed
DFT Prediction of Enhanced Reducibility of Monoclinic Zirconia upon Rhodium Deposition
2018
Oxides are an important class of materials and are widely used, for example, as supports in heterogeneous catalysis. In a number of industrial catalytic processes, oxide supports actively participate in chemical transformations by releasing lattice oxygen anions. While this is intuitively understood for reducible oxides, the reducibility of irreducible oxides may be modified via nanoengineering or upon inclusion of foreign species. Our calculations predict that the ability of irreducible monoclinic zirconia to release oxygen improves substantially upon deposition of rhodium. Through a comprehensive screening of Rh/ZrO2 with different size of the rhodium species, we find that a Rh adatom and…
Computational studies of gold-absorbate complexes on modified oxides
2016
While bulk gold is known for its chemical inertness, nanosized gold clusters are active catalysts for a variety of important reactions. For some practical applications gold clusters are supported and the cluster-support interaction can modify the cluster's properties. The knowledge of this interaction can be vital for obtaining desired cluster properties. In this thesis, the adsorption of Au atoms and clusters on modified oxide surfaces is studied using density functional theory (DFT) calculations. The support effects are considered by direct analysis of the adsorbed Au and using other coadsorbates as reactivity probes. Doping the CaO(001) surface by replacing a cation with a high valence d…
Production of ethyl lactate by activated carbon-supported Sn and Zn oxide catalysts utilizing lignocellulosic side streams
2021
In this study, activated carbon-supported Sn and Zn oxide catalysts were prepared from hydrolysis lignin and used for the conversion of model solutions of trioses, hexoses, and lignocellulosic biomass hydrolysates to ethyl lactate. Both catalysts, SnO2@AC and ZnO@AC, were able to produce ethyl lactate in high yields. SnO2@AC was a more active and selective catalyst in triose (dihydroxyacetone) conversion, providing 99% yield to ethyl lactate. ZnO@AC, by contrast, was more selective in glucose and hydrolysate conversion, with a yield of 60% and 85%, respectively. The ethyl lactate yields were significantly higher than those from the optimized model solution experiments when using ZnO@AC cata…
Dioxidomolybdenum(VI) and –tungsten(VI) complexes with tetradentate amino bisphenolates as catalysts for epoxidation
2017
Sixteen molybdenum and tungsten complexes with tripodal or linear tetradentate amino bisphenol ligands were studied as catalysts for the epoxidation of cis-cyclooctene, 1-octene, styrene, limonene and α-terpineol. These complexes can be divided into different categories upon key features, i.e. central metal (Mo versus W), side-arm donor (O versus N), hybridization of the N-donor (pyridine versus amine), ligand geometry (tripodal versus linear diamine) and sterical hindrance (Me versus tert-Bu substituents in the phenol part). All complexes can catalyse selectively the epoxidation of cis-cyclooctene by tert-butylhydroperoxide whereas the activities and selectivities towards other olefins (1-…
Cyclic Sulfoximine and Sulfonimidamide Derivatives by Copper‐Catalyzed Cross‐Coupling Reactions with Elemental Sulfur
2023
Copper-catalyzed cross-coupling reactions of α-bromoaryl NH-sulfoximines with elemental sulfur lead to benzo[d][1,3,2]dithiazole-1-oxides, which represent a new class of three-dimensional heterocycles. The reactions proceed under mild conditions showing good functional group and heterocycle tolerance. By imination/oxidation, the initial cross-coupling products can be converted to unprecedented cyclic sulfonimidamides derivatives. Furthermore, a seven-membered heterocycle was obtained by a ruthenium-catalyzed ring-expansion with ethyl propiolate. peerReviewed
Selective Synthesis of Z -Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones
2021
Journal of the American Chemical Society : JACS 143(22), 8375-8380 (2021). doi:10.1021/jacs.1c01797