Search results for "Enantioselective"
showing 10 items of 427 documents
Synthesis of an enantiopure 2-arylcyclohexanols from prochiral enol acetates by an enantioselective protonation/diastereoselective reduction sequence
2003
Abstract The enantioselective protonation with 2-sulfinyl alcohols of lithium enolates of 2-arylcyclohexanones with different substituents on the phenyl group takes place with excellent enantioselectivities (89–99%). Chiral 2-phenylcyclohexanone and 2-arylcyclohexanones carrying electron donor substituents on the aromatic ring are converted into the corresponding trans -2-arylcyclohexanols by diastereoselective reduction with sodium naphthalenide in the presence of acetamide. The stereochemical integrity of the tertiary stereocenter is fully preserved using this reduction procedure. Interestingly, the chiral proton source is not consumed in the synthesis.
Organocatalytic Enantioselective Alkylation of Pyrazol-3-ones with Isatin-Derived Ketimines: Stereocontrolled Construction of Vicinal Tetrasubstitute…
2016
A quinine-derived thiourea catalysed the enantioselective addition of 4-substituted pyrazolones to isatin-derived ketimines, providing a variety of aminooxindole-pyrazolone adducts containing congested vicinal tetrasubstituted stereocentres with excellent outcomes (up to 98% yield, >20:1 dr and 98% ee).
Intramolecular Michael reaction of tert-butylsulfinyl ketimines: asymmetric synthesis of 3-substituted indanones.
2011
Aromatic tert-butylsulfinyl ketimines bearing a suitable Michael acceptor at the ortho position readily undergo an intramolecular conjugate addition achieving indanone derivatives in good yields and complete diastereoselectivity.
Organocatalytic enantioselective synthesis of 2,5,5-trisubstituted piperidines bearing a quaternary stereocenter. Vinyl sulfonamide as a new amine pr…
2020
An organocatalytic desymmetrizing intramolecular aza-Michael reaction with vinyl sulfonamides as nucleophilic nitrogen source has been devised for the synthesis of a new family of 2,5,5-trisubstituted piperidines bearing a quaternary sterocenter. The process takes place with excellent levels of enantioselectivity and moderate to good diastereoselectivity. The vinyl sulfonamide moiety can be removed by means of an ozonolysis reaction.
Evaluation of the enantioselective binding of imazalil to human serum albumin by capillary electrophoresis
2015
In this work, a methodology for the evaluation of enantioselective binding of imazalil (IMA) enantiomers to human serum albumin (HSA) that does not require the separation of free and bound to HSA fractions is developed. This methodology comprises the incubation of IMA–HSA designed mixtures for 30 min directly in the capillary electrophoresis system and the subsequent direct injection and chiral separation of IMA employing highly sulfated β-cyclodextrin as chiral selector and the complete filling technique. Two mathematical approaches were used to estimate apparent affinity constants (K1), protein binding and enantioselectivity (ES) for both enantiomers of IMA. Moderate enantioselective bind…
Determination of fluoxetine enantiomers in pharmaceutical formulations by electrokinetic chromatography-counter current technique
2012
In this work, an electrokinetic chromatography–counter current procedure for the separation of fluoxetine enantiomers using highly sulfated β-cyclodextrin was optimized and applied to the determination of the enantiomers in three pharmaceutical formulations according to the matrix features. Quality criteria were applied to facilitate its transferability to testing laboratories. Fluoxetine was used therapeutically as the racemate, although a stereospecificity associated with its interactions with the neuronal serotonin-uptake carrier was demonstrated. In this context, the development of enantioselective methods for the chiral analysis of pharmaceuticals allowing stereoisomer ratio estimation…
Organic carbonates as alternative solvents for asymmetric hydrogenation
2009
Organic carbonates like propylene carbonate (PC) or butylene carbonate (BC) belong to the class of aprotic, highly dipolar solvents (AHD). Interestingly, their potential as solvents for asymmetric catalysis has been overlooked for a long time. The aim of this work is to evaluate organic carbonates and other organic solvents like THF, CH2Cl2, and acetonitrile as well as members of the AHD-family (DMF, DMSO, etc.) as media for homogeneous asymmetric hydrogenation. For this reason cationic Rh-complexes based on chiral phosphine ligands were tested in the hydrogenation of typical benchmark substrates. In several trials, significant advantages of organic carbonates were found. In contrast to DMS…
Enantioselective copper-aminopyridine-catalyzed aza-Henry reaction with chelating N-(2-pyridyl)sulfonyl imines
2012
This article describes a copper-catalyzed aza-Henry reaction. Copper complexes of camphor-derived aminopyridines catalyze the addition of nitromethane to N-(2-pyridyl)sulfonyl aldimines to give the corresponding β-nitrosulfonamides with good yields and variable enantiomeric excesses (up to 83%). An example of transformation of these compounds into N-(2-pyridyl)sulfonyl-α-amino acids and deprotection of the sulfonamide with Mg–MeOH is provided. Chirality 24:441–450, 2012. © 2012 Wiley Periodicals, Inc.
Enantioselective Hydrogenation Catalysis Aided by a σ-Bonded Calix[4]arene to a P-Chirogenic Aminophosphane Phosphinite Rhodium Complex
2010
The first P-chirogenic aminophosphane−phosphinite (AMP*P) ligand (4a) supported on the upper rim of a calix[4]arene moiety was synthesized in two steps using the ephedrine methodology. Ligand 4a wa...
3.17 Synthetically Derived Auxiliaries: Phosphorus Derivatives
2012
This chapter aims to give an overall view of chiral-pool based asymmetric synthesis of organophosphorus compounds more particularly bearing the chirality on the phosphorus atom (P-stereogenic). The enantiomerically pure organophosphorus compounds can be obtained either by resolution of the racemate or by stereoselective synthesis using particularly ephedrine or sparteine as the main chiral auxiliaries and borane as a P(III)-protecting group.