Search results for "Addition reaction"
showing 10 items of 125 documents
Synthesis of new polydentate oxalamide-based ligands as chiral catalysts for the enantioselective addition of diethylzinc to benzaldehyde
2006
New polydentate oxalamide-based ligands have been studied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde
ChemInform Abstract: One-Pot Synthesis of Polysubstituted Indolizines by an Addition/Cycloaromatization Sequence.
2013
Indolizines carrying various substituents in positions 5-8 were obtained from readily available 2-(1H-pyrrol-1-yl)nitriles and α,β-unsaturated ketones or aldehydes in a one-pot procedure. Michael addition of the deprotonated aminonitriles to the acceptors followed by acid-catalyzed electrophilic cyclization produces 5,6-dihydroindolizine-5-carbonitriles. From these stable intermediates, substituted indolizines were obtained via base-induced dehydrocyanation.
ChemInform Abstract: First Reactions of 2,2′-Bisindolyls with Electrophilic Azo Compounds and Diethyl Mesoxalate.
2010
Conformations and some electronic properties of the 2,2′-bisindolyls 6 were calculated for the prediction of probable Diels-Alder reactivity, in analogy to previous work on 2-vinylindoles. First reactions with dienophiles revealed that compounds 6 did not participate in [4 + 2]cycloadditions but rather underwent simple electrophilic substitutions at the enamine function with, above all, some heterodienophiles. Erste Reaktionen von 2,2′-Bisindolylen mit elektrophilen Azoverbindungen und Diethylmesoxalat Zur Vorhersage moglicher Diels-Alder-Reaktionen an 2,2′-Bisindolylen 6 werden Berechnungen zur Konformation und uber elektronische Eigenschaften durchgefuhrt. Die erstmals durchgefuhrten Reak…
ChemInform Abstract: A Catalytic Highly Enantioselective Direct Synthesis of 2-Bromo-2-nitroalkan-1-ols Through a Henry Reaction.
2009
Highly enantiomerically enriched 2-bromo-2-nitroalkan-1-ols are prepared by direct condensation of aliphatic and aromatic aldehydes with bromonitromethane in the presence of a catalytic amount of copper(II) acetate and a C1-symmetric camphor-derived amino pyridine ligand.
ChemInform Abstract: A General Overview of the Organocatalytic Intramolecular Aza-Michael Reaction
2015
The organocatalytic intramolecular aza-Michael reaction gives access to enantiomerically enriched nitrogen-containing heterocycles in a very simple manner. Enals, enones, conjugated esters and nitro olefins have been employed as Michael acceptors, while moderate nitrogen nucleophiles such as sulphonamides, carbamates and amides have been shown to be appropriate Michael donors in this type of reaction. Additionally, the process has been performed under both covalent and non-covalent catalysis, with diaryl prolinols, imidazolidinones, thioureas and chiral binol phosphoric acids being the most frequently used catalysts. The level of efficiency reached with this protocol is demonstrated by the …
ChemInform Abstract: Radical Addition to Iminium Ions and Cationic Heterocycles
2015
Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta react…
ChemInform Abstract: Stereoselective Nucleophilic Addition Reactions of Reactive Pseudopeptides.
2010
Highly Diastereoselective Michael Reaction of (S)‐Mandelic Acid Enolate. Chiral Benzoyl Carbanion Equivalent Through an Oxidative Decarboxylation of …
2002
The reaction of the lithium enolate of the 1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with α,β-unsaturated carbonyl compounds proceeds readily to give the corresponding Michael adducts in good yields and high diastereoselectivity. Subsequent basic hydrolysis of the acetal and oxidative decarboxylation of the α-hydroxyacid moiety provides chiral 2-substituted 1,4-dicarbonyl compounds with very high enantiomeric excesses.
Enantioselective synthesis of 2-substituted-1,4-diketones from (S)-mandelic acid enolate and α,β-enones
2006
[EN] An approach for the synthesis of chiral non-racemic 2-substituted-1,4-diketones from (S)-mandelic acid and ¿,ß-enones has been developed. The reaction of lithium enolate of the 1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with ¿,ß-unsaturated carbonyl compounds proceeds readily to give the corresponding Michael adducts in good yields and with high diastereoselectivities. The addition of HMPA (3 equiv) reverses and strongly enhances the diastereoselectivity of the reaction. A change in the reaction mechanism from a lithium catalyzed to the one where catalysis has been suppressed by coordination of HMPA to lithium is proposed to explain these resul…
Ferrocenylbis(ylene) phosphoranes
1997
The ferrocenylbis(methylene)phosphorane Fc-P(=CTms 2 ) 2 ( 1 ) (Fc = −C 5 H 4 FeC 5 H 5 ) can be synthesized starting from ferrocenyldichlorophosphane FcPCl 2 or ferrocenyldilithiophosphane FcPLl 2 . The X-ray structure of ( 1 ) shows some unusual structural features, which indicate considerable electronic interaction of the ferrocenyl group and the σ 3 λ 5 -phosphorane unit. As a consequence of this interaction, the rotational barrier of the methylene bonds is extraordinary low. Therefore, in contrast to other bis(methylene)phosphoranes, the endo - and exo -Tms groups are indistinguishable on the NMR time scale even at −100°C. The analogous ferrocenylbis(imino)phosphorane Fc-P(=NTms) 2 ( 9…