Search results for "HYDROLYSIS"
showing 10 items of 632 documents
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 …
Reactivity of lithium β‑ketocarboxylates: the role of lithium salts
2017
Lithium beta-ketocarboxylates 1(COOLi), prepared by the reaction of lithium enolates 2(Li+) with carbon dioxide, readily decarboxylate in THF solution unless in the presence of lithium salts, in which case they are indefinitely stable at room temperature in inert atmosphere. The availability of stable THF solutions of lithium beta-ketocarboxylates 1(COOLi) in the absence of carbon dioxide allowed reactions to take place with nitrogen bases and alkyl halides 3 to give alpha-alkyl ketones 1(R) after acidic hydrolysis. The sequence thus represents the use of carbon dioxide as a removable directing group for the selective monoalkylation of lithium enolates 2(Li+). The roles of lithium salts in …
Crystal Engineering Applied to Modulate the Structure and Magnetic Properties of Oxamate Complexes Containing the [Cu(bpca)]+ Cation
2016
This work deals with the crystal engineering features of four related copper(II)-based compounds with formulas {[{Cu(bpca)}2(H2ppba)]·1.33DMF·0.66DMSO}n (2), [{Cu(bpca)(H2O)}2(H2ppba)] (3), [{Cu(bpca)}2(H2ppba)]·DMSO (4), and [{Cu(bpca)}2(H2ppba)]·6H2O (5) [H4ppba = N,N′-1,4-phenylenebis(oxamic acid) and Hbpca = bis(2-pyridylcarbonyl)amide] and how their distinct molecular and crystal structures translate into their different magnetic properties. 2 and 3 were obtained through the hydrolytic reaction of the double-stranded oxamato-based dipalladium(II) paracyclophane precursor of formula [{K4(H2O)2}{Pd2(ppba)2}] (1) with the mononuclear copper(II) complex [Cu(bpca)(H2O)2]+, either in a water…
Synthesis of l -[4-11 C]Asparagine by Ring-Opening Nucleophilic 11 C-Cyanation Reaction of a Chiral Cyclic Sulfamidate Precursor
2018
The development of a convenient and rapid method to synthesize radiolabeled, enantiomerically pure amino acids (AAs) as potential positron emission tomography (PET) imaging agents for mapping various biochemical transformations in living organisms remains a challenge. This is especially true for the synthesis of carbon-11-labeled AAs given the short half-life of carbon-11 (11 C, t1/2 =20.4 min). A facile synthetic pathway to prepare enantiomerically pure 11 C-labeled l-asparagine was developed using a partially protected serine as a starting material with a four-step transformation providing a chiral five-membered cyclic sulfamidate as the radiolabeling precursor. Its structure and absolute…
Formation of Aroma by Hydrolysis of Glycosidically Bound Components
1992
SUMMARY Acid hydrolysis has been used in order to establish the presence of glycosidically bound components in fruits. During this treatment, rearrangement reactions of free monoterpene alcohols generally occur. This inconvenient may be avoided using enzymatic hydrolysis, however the specificity of enzymes requires the previous knowledge of the structures of compounds used as substrates in order to control the reaction. Several glycosidically bound components, glucosides, rutinosides and arabinoglucosides present in grapes and apricot were isolated, separated and identified using non destructive methods, MS-MS low energy CAD spectra and HPLC. s-D-glucosidase, α-L-rhamnosidase, α-L-arabinase…
Peptide synthesis with 5-amino-1-methyl-1H-[1,2,4]triazole-3-carboxylic acid
2007
Abstract In the search for the peptide synthesis of new potential lexitropsins, starting with methyl 5‐amino‐1‐methyl‐1H‐[1,2,4]triazole‐3‐carboxylate 1a, we synthesized the chloroacetyl derivative of 2a, which was hydrolyzed to acid 2b and ammonolyzed to the peptide 2c. A more effective route was the use of (t‐butoxycarbonyl)glycyl‐benzotriazolide 3 to the acylation 1a, which leads the N/C protected peptide 4. This peptide was selectively N‐deprotected to be the useful segment 5 for further peptide syntheses to the N‐terminus. It was also C‐deprotected, that is hydrolyzed to give peptide 2c for further C‐extension. To the best of our knowledge, this is the first peptide that is a derivativ…
New Strategies for the Synthesis of Fluorinated Vinylogous Amidines and β-Enamino Ketones
2001
Reaction of fluorinated imidoyl chlorides 3 with ketimines 1a provides fluorinated 1,3-diimines, which were exclusively isolated as vinylogous amidine tautomers 2beta, with good yields. Fluorinated beta-enamino ketones 4 are obtained by regioselective hydrolysis of 2. Complementary methods for the synthesis of regioisomeric beta-enamino ketones 4 and 5 are also reported. These methods include the reaction of azaenolates of ketimines with fluorinated esters 6 and reactions of ketone enolates with fluorinated imidoyl chlorides 3. The behavior of these systems in hydrolysis reactions was also tested.
α-L-rhamnosidases: Old and New Insights
2007
L-Rhamnose is a component of plant cell wall pectic polysaccharides (Mutter et al., 1994; Ridley et al., 2001), glycoproteins (Haruko and Haruko, 1999) and secondary metabolites such as anthocyanins (Renault et al., 1997), flavonoids (Bar-Peled et al., 1991) and triterpenoids (Friedman and McDonald, 1997). It has also been found in bacterial heteropolysaccharides (Hashimoto and Murata, 1998), rhamnolipids (Ochsner et al., 1994) and in the repeating units of the O-antigen structure of the lipopolysaccharide component of bacterial outer membranes (Chua et al., 1999). Some rhamnosides are important bioactive compounds, e.g. cytotoxic saponins (Bader et al., 1998; Yu et al., 2002), antifungal p…
Hydrolysis of (CH3)Hg+ in Different Ionic Media: Salt Effects and Complex Formation
1998
The hydrolysis of monomethylmercury(II) was studied potentiometrically, in NaNO3, Na2SO4, and NaCl aqueous solution, in a wide range of ionic strengths (NaNO3, 0 ≤ I ≤ 3.25; Na2SO4, 0 ≤ I ≤ 1; NaCl, 0 ≤ I ≤ 3 mol dm-3) and at t = 25 °C. For the reaction (CH3)Hg+ = (CH3)Hg(OH)° + H+, we found log K1 = −4.528 (I = 0 mol dm-3). The species [(CH3)Hg]2(OH)+ was also found, with log β2 = −2.15. Monomethylmercury(II) forms quite strong complexes with Cl- (log K = 5.45, I = 0 mol dm-3) and SO42- (log K = 2.64, I = 0 mol dm-3). The dependence on ionic strength of formation constants was considered by using a Debye−Huckel type equation. Hydrolysis and complex formation constants (at different ionic s…
Enzymatische hydrolyse hydrophiler ester durch lipasen - eine milde carboxydeblockierung von peptiden und glycopeptiden
1993
Abstract The markedly hydrophilic 2-(N-morpholino)ethyl (MoEt) esters of protected peptides and glycopeptides are selectively and efficiently cleaved by lipases in water/acetone (10:1) at pH 7.