Search results for "enantiomeric excess"

Synthesis of Chiral Catalyst Modifiers by Hydrosilylation of Cinchonidine and Their Application in the Hydrogenation of 1-Phenylpropane-1,2-dione and…

2005

Four new chiral modifiers were synthesized in order to investigate the effect of distal modifier substitution in the hydrogenation of ethyl pyruvate and 1-phenylpropane-1,2-dione on a supported Pt/Al2O3 catalyst. The chiral modifiers were prepared in good to moderate overall yields by Pt-catalyzed hydrosilylation of 9-O-TMS-protected cinchonidine with triethylsilane, triphenylsilane, bis(dimethylsilyl)ethane and (+)-(R)-methyl(1-naphthyl)phenylsilane followed by cleavage of the silyl ether protective group. Comparison of the synthesized modifiers in enantioselective hydrogenation using cinchonidine as reference modifier is reported, as well as details on their synthesis and characterization…

Kinetische Racematspaltungen ausgehend vonrac-Alkoholen oderrac-Carbonsäurehalogeniden unter Mitwirkung optisch aktiver Induktorbasen

1989

Bei der Umsetzung eines Molaquivalents achiraler Carbonsaurehalogenide mit zwei Molaquivalenten rac-Alkoholen entstehen unter Mitwirkung von einem Molaquivalent einer optisch aktiven Induktorbase (tertiares Amin) partiell optisch aktive Ester sowie partiell optisch aktive Alkohole in zum Teil hoher optischer Reinheit (60 – 70%). Der im Ester gebundene Anteil an Alkohol sowie der nicht umgesetzte Alkohol haben entgegengesetzte Konfiguration. Der Induktionsgrad ist ahnlich hoch, wenn man zwei Molaquivalente eines rac-Carbonsaurehalogenids mit je einem Molaquivalent eines achiralen Alkohols und einer Induktorbase umsetzt. Der Carbonsaureanteil im Ester und die freie Saure haben entgegengesetzt…

Enantioselective LaIII-pyBOX-Catalyzed Nitro-Michael Addition to (E)-2-Azachalcones

2013

A [La(OTf)3] complex with a new pyBOX ligand bearing a bulky 1-naphthylmethyl substituent at the 4′-position of the oxazoline ring catalyzes the conjugate addition of nitroalkanes to a broad range of (E)-2-azachalcones, providing the expected nitro-Michael products with good yields and enantiomeric excesses up to 87 %. The optical purity of the products can be increased by a single crystallization. A plausible stereochemical model to account for the observed stereochemistry has been proposed.

Stereoselective Synthesis and Pharmacological Evaluation of 2,4-Bridged Piperidine Derivatives Designed to Activate the κ-Opioid Receptor

2021

Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium-Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates

2015

The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium-catalyzed aminocarbonylation reaction of the corresponding -fluoroalkyl o-iodobenzylamines. A base-mediated anti -hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine-tuning the pK(a) of the base.

From Overstoichiometric to Substoichiometric Enantioselective Protonation with 2-Sulfinyl Alcohols: A View in Perspective

2005

A general study of the enantioselective protonation of prochiral enolates with 2-sulfinyl alcohols is reported. The modification of reaction conditions to reduce drastically the amount of chiral proton source needed to obtain a good enantiomeric excess is reported. The effects of the different factors controlling the stereoselectivity are clearly established. Different protocols for enolate generation are compared.

Lipase-catalyzed resolution of β-hydroxy selenides

2006

Abstract Eleven β-hydroxy selenides were kinetically resolved using an immobilized lipase (Amano PS-C II) in toluene in the presence of vinyl acetate at 30 °C. This approach provided, in several cases, both enantiomers in high enantiomeric excess. The role of the size of substituents and the behaviour of cyclic β-hydroxy selenides is also discussed. Enantiopure β-hydroxy selenides are useful building blocks. As an application of this chemistry, enantiopure (1 S ,2 R )-indene oxide was obtained in one step from the proper enantiopure β-hydroxy selenide.