Search results for "stereoselectivity"
showing 5 items of 325 documents
Applications and stereoselective syntheses of P-chirogenic phosphorus compounds.
2016
International audience; Phosphorus compounds bearing chirality on the P-center are usually qualified as P-chirogenic or P-stereogenic. This chemical class concerns natural products, agrochemistry, molecular materials, biology and pharmacy, although it is certainly in coordination chemistry and in asymmetric catalysis using chiral transition metal complexes that P-chirogenic phosphorus compounds are the most used. The chiral phosphine ligands and their uses in asymmetric metal-catalyzed reactions have been widely reviewed in literature. However, an overview covering the applications as well as the stereoselective syntheses of all classes of phosphorus compounds has not yet been provided. Thi…
Understanding the stereoselectivity in Brønsted acid catalysed Povarov reactions generating cis/trans CF3-substituted tetrahydroquinolines: a DFT stu…
2016
The Bronsted acid (BA) catalysed Povarov reactions of (E)-1-phenyl-N-(4-(trifluoromethyl)phenyl) methanimine with 1-vinylpyrrolidin-2-one (VPO) and with allyltrimethylsilane (ATMS), affording CF3-substituted cis/trans tetrahydroquinoline (THQ) derivatives, have theoretically been studied using the M06-2X functional together with the standard 6-31G(d) basis set. These BA catalysed Povarov reactions are multistep processes initialised by the nucleophilic attack of the non-substituted carbon atom of the nucleophilic ethylene on the imine carbon atom of the super-electrophilic protonated imine, yielding the corresponding cationic intermediate along the endo/exo stereoisomeric approach mode. Upo…
A Highly Regio-, Diastereo- and Enantioselective Intramolecular Cyclopropanation Reaction of a Racemic α-Diazo Ketone Catalyzed by Chiral ortho-Metal…
2003
Abstract A series of racemic dirhodium(II) compounds with two ortho-metalated aryl phosphine ligands in a head-to-tail arrangement Rh2(O2CR)2(pc)2 (pc=ortho-metalated aryl phosphine) (1a–k) were tested in the regio- and stereoselective cyclopropanation of racemic 1-diazo-6-methyl-3-(2-propenyl)-5-hepten-2-one 2, which possesses two different reactive CC double bonds for a five-membered-ring formation. The complexes Rh2(O2CCH3)2(pc)2 {pc=[(C6H4)P(C6H5)2], [(p-CH3C6H3)P(p-CH3C6H4)2], and [(C6H4)P(C6H5)(C6F5)]} (1a–d) successfully enhanced the cyclopropanation of trisubstituted versus monosubstituted CC bonds to give an 80:20 selectivity ratio. The reaction occurred with excellent diastereos…
Synthesis of Trisaccharides by Hetero-Diels–Alder Welding of Two Monosaccharide Units
2012
A new strategy for the synthesis of di- and trisaccharides based on the de novo synthesis of the linking saccharide unit is presented. In this strategy, functionalized monosaccharide building blocks already incorporating the glycosidic linkages are welded together using a metal-catalyzed hetero-Diels–Alder (HDA) reaction to generate a new monosaccharide unit between them. The highest yields and selectivities in the HDA reaction were obtained by using chiral Schiff base chromium complexes. Disaccharide products were accessible by reaction of Danishefsky's diene with acetyl- and benzyl-protected galactoside aldehydes. For the synthesis of trisaccharide products, acetyl-protected glucose or ga…
Hydrophobically Directed Aldol Reactions: Polystyrene-SupportedL-Proline as a Recyclable Catalyst for Direct Asymmetric Aldol Reactions in the Presen…
2007
The cover picture shows the aldol reaction between ketones and arylaldehydes carried out by using a polystyrene-supported L-proline catalyst. This material furnishes aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water. This solvent effect, coupled with the high stereoselectivities observed, has been explained by the formation of a hydrophobic core in the inner surface of the resin with the hydrophilic proline moiety in the resin/water interface. Such a microenvironment promotes the aldol reaction and increases the stereoselectivity. Recycling investigations have shown that this material can be reus…