Search results for "Racemi"

Unusual packing of ET molecules caused by π–π stacking interactions with TRISPHAT molecules in two [ET][TRISPHAT] salts (ET=bis(ethylenedithio)tetrat…

2007

Abstract The synthesis, structure and physical properties of two new radical salts formed with the organic donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) and a racemic mixture of the chiral anion (tris(tetrachlorobenzenediolato)phosphate(V)) (TRISPHAT) are reported. The structure of the salts (ET)4[TRISPHAT]4 · 3.5H2O (1) and (ET)(TRISPHAT) · CH2Cl2 · CH3CN (2) has been solved by X-ray single crystal diffraction. Unusual packings of ET molecules are obtained in the two structures. The electrical properties indicate that both compounds are insulators. This is in agreement with the isolation of the ET molecules and their complete ionization. On the other hand, the anisotropy of …

Stereoselective synthesis of o-bromo (or iodo)aryl P-chirogenic phosphines based on aryne chemistry.

2012

The efficient synthesis of chiral or achiral tertiary phosphines bearing an o-bromo (or iodo)aryl substituent is described. The key step of this synthesis is based on the reaction of a secondary phosphine borane with the 1,2-dibromo (or diiodo)arene, owing to the formation in situ of an aryne species in the presence of n-butyllithium. When P-chirogenic secondary phosphine boranes were used, the corresponding o-halogeno-arylphosphine boranes were obtained without racemization in moderate to good yields and with ee up to 99%. The stereochemistry of the reaction, with complete retention of the configuration at the P atom, has been established by X-ray structures of P-chirogenic o-halogenopheny…

Racemization of Secondary-Amine-Containing Natural Products Using Heterogeneous Metal Catalysts

2018

Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4– Nanoclusters via Ion Pairing

2016

In this work, a facile ion-pairing strategy for asymmetric synthesis of optically active negatively charged chiral metal nanoparticles using chiral ammonium cations is demonstrated. A new thiolated chiral three-concentric-shell cluster, [Ag28Cu12(SR)24]4–, was first synthesized as a racemic mixture and characterized by single-crystal X-ray structure determination. Mass spectrometric measurements revealed relatively strong ion-pairing interactions between the anionic nanocluster and ammonium cations. Inspired by this observation, the as-prepared racemic mixture was separated into enantiomers by employing chiral quaternary ammonium salts as chiral resolution agents. Subsequently, direct asymm…

Dicarbonylchloro(pentabenzylcyclopentadienyl)ruthenium as Racemization Catalyst in the Dynamic Kinetic Resolution of Secondary Alcohols

2009

Dicarbonylchloro(pentabenzylcyclopentadienyl)ruthenium has been prepared and its structure confirmed by X-ray analysis. This complex shows excellent catalytic activity and modest stability against air in racemization reactions of secondary alcohols. In Candida antarctica lipase B (CAL-B) catalyzed dynamic kinetic resolution (DKR) of 1-phenyl- and 1-(furan-2-yl)ethanol compounds, the new complex shows improved performance as an alcohol racemization catalyst in comparison with its well-known pentaphenylcyclopentadienyl analogue, hitherto considered as the leading catalyst candidate. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Designing Silylatedl-Amino Acids using a Wittig Strategy: Synthesis of Peptide Derivatives and18F-Labelling

2017

An efficient semisynthesis of silylated l-amino acids by reaction of silylated benzaldehydes with a phosphonium l-amino acid used as a Wittig reagent is described. The efficiency of the silylated l-amino acids in peptide synthesis was investigated by coupling both the carboxylic acid and the amino moiety with l-alanine and phenylalanine derivatives, respectively. The silylated derivatives were treated with KF or tetrabutylammonium fluoride to give the corresponding fluorosilyl derivatives without racemization. The hydrolysis of the fluorosilylated derivatives in phosphate buffer at pH 7.2 was checked. Finally, the 18F-labelling of di-tert-butylsilylated saturated and unsaturated dipeptides …

Palladium-Catalyzed Reaction of Boronic Acids with Chiral and Racemic ?-Bromo Sulfoxides.

2005

Palladium-catalyzed cross-coupling reactions of racemic α-bromo sulfoxides with boronic acids are carried out in either aqueous or nonaqueous medium with formation of a new C sp3−C sp2 bond. The arylation of chiral α-bromo sulfoxides occurs without racemization. The cross-coupling reaction is general and gives high yields with arylboronic acids substituted with either donor or acceptor groups but gives poor results with heteroarylboronic acids. The best yields are obtained using degassed solvents and CsF instead of aqueous base. The use of aqueous base and the presence of oxygen favor the homocoupling side reaction.

Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (1014)

2012

Chirality can have a decisive influence on the molecular structure formation upon self-assembly on surfaces. In this paper, we study the structures formed by enantiopure (M)-heptahelicene-2-carboxylic acid ((M)-[7]HCA) on the calcite (10 (1) over bar4) cleavage plane under ultrahigh vacuum conditions. Previous noncontact atomic force microscopy studies have revealed that the racemic mixture of (M)-[7]HCA and (P)-[7]FICA (1:1) self-assembles into well-defined molecular double rows that are oriented along the calcite [01 (1) over bar0] direction. Here, we investigate the enantiopure (M)[7]HCA compound, resulting in distinctly different molecular structures upon deposition onto calcite (10 (1)…

Organo-phosphorus compounds—LXVI

1970

Abstract The recemization kinetics of (+)-methyl-n-propylphenylphosphine were studied in several solvents of widely varying polarity. The recemization followed first order kinetics in every solvent with approximately equal activation energies of 30 ±3 kcal/mole. The rate of racemization showed no dependence on solvent polarity and could not be correlated with any known solvent parameters. The unusually slow racemization in caproic acid and in tributyl borate were attributed to partial salt and adduct formation respectively.

Das System 2‐Halogenethylester/Cholinester als Zweistufen‐Schutzgruppe für die Carboxylfunktion von Aminosäuren und Peptiden

1979

Das System 2-Chlorethyl- und 2-Bromethylester/Cholinester wird als Carbonsaure-Schutzfunktion beschrieben. Die 2-Chlorethyl-(OEt(Cl))- und die 2-Bromethylester (OEt(Br)) der Aminosauren (4) lassen sich einfach herstellen und mit Z- und Boc-Aminosauren zu Z- und Boc-Dipeptidestern 5 und 6 verknupfen. Die Esterfunktionen sind gegen nicht zu stark saure und basische Einflusse bestandig. Sie konnen mit Natriumiodid in DMF in 2-Iodethylester 8 ubergefuhrt werden, welche mit Zink in einer Eintopfreaktion spaltbar sind. Durch Umsetzung mit Trimethylamin gehen die hydrophoben 2-Halogenethylester in die hydrophilen Cholinester 10 und 11 uber. Diese sind sehr stabil gegen Sauren. Sie konnen in wasrig…