Search results for "Protonation"

Synthesis of (–)-(S)-Norlaudanosine, (+)-(R)-O,O-Dimethylcoclaurine, and (+)-(R)-Salsolidine by Alkylation of an α-Aminonitrile

2007

A short asymmetric synthesis of 1-substituted 1,2,3,4-tetrahydroisoquinoline alkaloids by deprotonation of an unprotected α-aminonitrile and alkylation of the resulting carbanion followed by spontaneous elimination of HCN and asymmetric reduction is described. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

ChemInform Abstract: A Short Synthesis of Pyridines from Deprotonated α-Aminonitriles by an Alkylation/RCM Sequence.

2016

A short synthesis of pyridines from deprotonated α-aminonitriles by an alkylation/RCM sequence

2016

Abstract α-Aminonitriles can serve as versatile key precursors for the synthesis of nitrogen containing heterocycles. After unsuccessful trials involving the [1,2]-Stevens rearrangement of nitrile-stabilized ammonium ylides, we herein report a simple three-step synthesis of substituted pyridines based on an alkylation/ring-closing metathesis/aromatization sequence.

13C NMR studies of dianions of unsaturated carboxylic acids

1994

Abstract 13C NMR Spectra of the dianions Li2-n resulting from double deprotonation of unsaturated carboxylic acids 1 to 6 by lithium dialkylamides, are examined. Higher field resonance for C2 than for C4 atoms are observed, which reveal higher elctron density at C2 than at C4, in agreement with the kinetic α-regioselectivity exhibited by these dianions on reaction with electrophiles.

Flow-injection spectrophotometric determination of arylamines and sulphonamides by diazotization and coupling in a micellar medium

1991

Abstract In a sodium dodecyl sulphate (SDS) micellar solution, the rate of coupling of a diazonium ion with N-(1- naphthyl)ethylenediamine (NED) increases greatly, the protonation of the resulting azo dyes takes place at higher pH values and the dyes are more soluble. These favourable features were applied to the development of a simple flow-injection spectrophotometric procedure for the determination of diazotizable substances of pharmaceutical interest. Limits of detection in the range 0.2–0.5 μg ml−1 (signal-to-noise ratio=3), with relative standard deviation of 0.7–3% (n=3) for 5 μg ml−1 standards, were obtained.

Theoretical study on hydration of two particular diazanaphthalenes

2005

Abstract Cinnoline (1) and Phthalazine (2), diazanaphthalenes involved in certain biological reactions, have been studied computational with the purpose of comparing their protonation and covalent hydration mechanisms. Geometry optimizations of neutral, mono- and di-protonated cations and hydrated products were performed at HF, DFT/B3LYP levels of theory using 6-311G* basis set and single points energies were calculated at the MP2 level of theory using the same basis set. In agreement with experimental results, calculations predict a two-step mechanism resulting in a hydrated cation in which the OH of the water is located depending on the position of both nitrogen in the diazanaphthalene mo…

Deprotonation of resorcinarenes by mono- and diamine bases: complexation and intermolecular interactions in the solid state

2014

The deprotonation of resorcinarenes by mono- and dibasic amines, viz. triethylamine (TEA) and its dibasic analogue, N,N′-dimethylpiperazine (DMPip), was studied and the resulting supramolecular complexes were analysed in the solid state, in solution and in the gas phase. In the solid state, 1:1 (2TEAH+·(ethyl-resorcinarene)2−·MeOH), 3:2 [DMPip·2DMPipH+·2(ethyl-resorcinarene−)] and 3:2 [2DMPip·DMPipH22+@(2methyl-ethyl-resorcinarene−)2·2MeOH] solid state complexes and interesting resorcinarene−⋯resorcinarene− supramolecular networks formed via enhanced hydrogen bonds involving the hydroxyl groups and the deprotonated hydroxyl groups of the resorcinarenes were observed. The host–guest complexe…

Acridine orange in a pumpkin-shaped macrocycle: Beyond solvent effects in the UV–visible spectra simulation of dyes

2010

Abstract We present simulation of the UV–visible spectra of acridine orange, a widely used photosensitizer for in vivo studies due to its highly environment-dependent spectroscopic properties. This dye has been investigated both in its protonated and neutral forms, either isolated or embedded in a pumpkin-shaped macromolecular cycle (cucurbit-7-uril), using time-dependent density functional theory techniques. To model this macromolecular cycle, two strategies are taken into account, allowing decoupling of the geometric and electrostatic influences of the host on the guest molecules. Experimental data are well-reproduced when using an embedding electrostatic technique, suggesting that such a…

Asymmetric Homoaldol Reactions with Cyclohex-2-enylN,N-Diisopropylcarbamate: Kinetic Resolution, Elucidation of the Stereochemical Course and Applica…

2007

Enantio-enriched cyclohex-2-enyl N,N-diisopropylcarbamate (5) is stereospecifically deprotonated by sec-butyllithium/(–)-sparteine (9) to form the configurationally stable lithium complex 7·9. A kinetic resolution of rac-5 by n-butyllithium/(–)-sparteine (9) yielded (R)-5 with up to 99 % ee. Electrophilic substitution with tin electrophiles proceeds in a anti-SE′ fashion as shown by chemical correlations. The synthesized allylstannanes 10 undergo a highly stereospecific TiCl4-mediated homoaldol reaction with various aldehydes, yielding syn-configured homoaldol products 12. These were transferred into all-cis-configured hexahydroisobenzofuran-4(1H)-ones 22 by BF3·OEt2-mediated reactions with…

From over-stoichiometric to sub-stoichiometric 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. Medio Simon, Mercedes, Mercedes.Medio@uv.es ; Aleman Lopez, Pedro Antonio, Pedro.Aleman@uv.es ; Gil Tomas, Jesus Javier, Jesus.J.Gil@uv.es ; Asensio, Aguilar Gregorio, Gregorio.Asensio@uv.es