Search results for "ketone"
showing 10 items of 337 documents
Understanding the regio- and chemoselective polar [3+2] cycloaddition of the Padwa carbonyl ylides with α-methylene ketones. A DFT study
2009
The regio- and chemoselective polar [3+2] cycloaddition (32CA) of the Padwa carbonyl ylide (CY) with α-methylene ketone (αMK) to yield the oxa-bridged spirocycloadduct has been studied using the DFT method at the B3LYP/6-31G(d) computational level. Six reactive channels associated to the stereo-, regio-, and chemoselective approach modes of the CY to the CC and CO reactive sites of the αMK have been analyzed. DFT calculations for this cycloaddition are in complete agreement with the experimental outcome, explaining the reactivity and selectivity of the formation of the [3+2] cycloadduct. Analysis of the global and local electrophilicity and nucleophilicity indices allows an explanation abou…
Hantzsch Ester-Mediated Photochemical Transformations in the Ketone Series: Remote C(sp3)–H Arylation and Cyclopentene Synthesis through Strain Relea…
2021
A metal-free Hantzsch ester-mediated synthesis of cyclopentenylketones as well as γ-hetarylketones starting from ketocyclopropanes under eco-friendly conditions was developed. The versatility of the developed conditions is shown by reacting ketocyclopropanes in both a formal [3 + 2] cycloaddition with terminal alkynes (further investigated using theoretical calculations) and a radical C-C-coupling with cyanopyridines. The newly developed methodologies were later on utilized as a downstream reaction for photogenerated cyclopropanes combining UV and visible light photochemistry. Following this procedure, a UV-driven Norrish-Yang-type reaction induces the ring strain of the intermediates, whic…
Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures with Cyclohexane, Cyclohexene, and Methyl Isobutyl Ketone at 100 kPa
2010
Consistent vapor−liquid equilibrium (VLE) data at 100 kPa have been determined for the ternary system cyclohexane + cyclohexene + methyl isobutyl ketone and two constituent binary systems: cyclohexane + methyl isobutyl ketone and cyclohexene + methyl isobutyl ketone. Both binary systems show positive deviations from ideal behavior and do not present an azeotrope. The VLE data have been correlated by the Wilson, UNIQUAC, and NRTL equations. The ternary system does not present an azeotrope and is well predicted from binary interaction parameters. Prediction with the UNIFAC method has also been obtained.
First reactions of dialkoxycarbenium tetrafluoroborates with pyrroles, 5H-dibenz[b,f]azepines, and electron-rich arenes
2009
Pyrrole (2a) and 2,5-dimethylpyrrole (2b) react with the dialkoxycarbenium tetrafluoroborates 1a-1c under kinetic control to yield the corresponding acylpyrrole derivatives. 5H-Dibenz[b,f]azepine (9a) and the 10,11-dihydro derivative 9b react only with the most electrophilic of the series of electrophiles tested, namely, diethoxycarbenium tetrafluoroborate (1a), to furnish the corresponding formyl derivatives. Similarly, in arene chemistry, the highly electron-rich N,N-dimethylaniline (13a) and 1,3,5-trimethoxybenzene (13b) are formylated by reaction with 1a.
An approach to erythrophleum alkaloids. Synthesis of methyl (−)-4-epi-cassamate
1986
Abstract A synthetic approach to Erythrophleum alkaloids, involving as a key-step the regiospecific deprotonation of the ketone 5a, is described.
Stereospecific CC-bond formation with rabbit muscle aldolase - A chemoenzymatic synthesis of (+)-exo-brevicomin
1990
Abstract (+)-(1S,5R,7S)-Exo-brevicomin 9, a sex pheromone of the western pine bark beetle, is synthesized using an aldol reaction catalyzed by fructose-1,6-diphosphate aldolase (EC 4.1.2.13) from rabbit muscle as the key step by which the absolute configuration of the target is established.
Synthesis of Optically Active N-(4-Hydroxynon-2-enyl)pyrrolidines: Key Building Blocks in the Total Synthesis of Streptomyces coelicolor Butanolide 5…
2021
AbstractStarting from 5-methylhexanal and (S)-configured N-propargylprolinol ethers, coupling delivered N-(4-hydroxynon-2-ynyl)prolinol derivatives as mixtures of C4 diastereomers. Resolution of the epimers succeeded after introduction of an (R)-mandelic ester derivative and subsequent HPLC separation. Alternatively, suitable oxidation gave the corresponding alkynyl ketone. Midland reagent controlled diastereoselective reduction afforded a defined configured propargyl alcohol with high selectivity. LiAlH4 reduction and Mosher analyses of the allyl alcohols enabled structure elucidation. The suitably protected products are used as key intermediates in enantioselective Streptomyces γ-butyrola…
Saturated vapour pressure of aroma compounds at various temperatures
2004
Abstract The aim of this study was to determine experimentally the vapour pressures of aroma compounds at various temperatures, especially at negative ones. The aroma compounds were: acetone, 2-butanone, 2-hexanone, 2-octanone, ethyl acetate, ethyl butanoate, ethyl hexanoate, n-hexanal, n-hexanol and γ-hexalactone. The technique used was a static device where vapour pressure was measured at equilibrium. The temperatures of analysis varied from −40 to 25 °C. Volatility of a pure compound depends on characteristics such as length of the aliphatic chain, the functional group and temperature. Among an homologous series, volatility increases when the aliphatic chain decreases and when temperatur…
Synthesis of Functionalized Indoles with an α-Stereogenic Ketone Moiety Through an Enantioselective Friedel-Crafts Alkylation with (E)-1,4-Diaryl-2-b…
2009
Chiral complexes of BINOL-based ligands with hafnium tert-butoxide catalyze the enantioselective Friedel-Crafts alkylation of indoles with (E)-1,4-diaryl-2-butene-1,4-diones at room temperature, with good yields and ee up to 94%. Hafnium(IV) was found to be a more effective Lewis acid than other frequently used metal ions such as titanium(IV) or zirconium(IV). Unlike the enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated compounds where the stereogenic center is generated in the β-position to a carbonyl group, the Friedel-Crafts alkylation with 2-butene-1,4-diones described here generates an α-stereogenic center with respect to one of the carbonyl groups. This can be…
4-Alkenyl-1,2,3-thiadiazole
1986
Die Titelverbindungen 5 werden aus entsprechenden Alkylderivaten durch Bromierung/Dehydrobromierung (Weg A) oder durch Wittig-Reaktion (Weg B) dargestellt. Mit 4-Phenyl-4H-1,2,4-triazol-3,5-dion entstehen unter Erhaltung des Thiadiazolrings die Monoaddukte 12. 4-Alkenyl-1,2,3-thiadiazoles The title compounds 5 are prepared from the corresponding alkyl derivatives by bromination/dehydrobromination (route A) or by Wittig reaction (route B). 4-Phenyl-4H-1,2,4-triazole-3,5-dione yields the monoadducts 12 by maintenance of the thiadiazole ring.