Search results for "Aminolysis"

The HMGB1 protein induces a metabolic type of tumour cell death by blocking aerobic respiration

2016

The high-mobility group box 1 (HMGB1) protein has a central role in immunological antitumour defense. Here we show that natural killer cell-derived HMGB1 directly eliminates cancer cells by triggering metabolic cell death. HMGB1 allosterically inhibits the tetrameric pyruvate kinase isoform M2, thus blocking glucose-driven aerobic respiration. This results in a rapid metabolic shift forcing cells to rely solely on glycolysis for the maintenance of energy production. Cancer cells can acquire resistance to HMGB1 by increasing glycolysis using the dimeric form of PKM2, and employing glutaminolysis. Consistently, we observe an increase in the expression of a key enzyme of glutaminolysis, malic …

Six-Step Gram Scale Synthesis of the HIV Integrase Inhibitor Dolutegravir Sodium

2021

A short and practical synthesis for preparing the active pharmaceutical ingredient dolutegravir sodium was investigated. The convergent strategy developed herein starts from 3-(R)-amino-1- butanol and builds up the BC ring system in 76% isolated yield over four steps. Ring A was constructed by a one-pot 1,4-addition to diethyl-(2E/Z)-2-(ethoxymethylidene)-3-oxobutandioate and subsequent MgBr2·OEt2-mediated regioselective cyclization. Amide formation with 2,4- difluorobenzylamine was either performed from the carboxylic acid or through aminolysis of the corresponding ester precursor. Final salt formation afforded dolutegravir sodium in 48–51% isolated yield (HPLC-purity: 99.7–99.9%) over six…

1986

The aminolysis of diphenyl terephthalate by means of hexylamine was studied in dimethyl sulfoxide as a model reaction for polyamidation. The kinetic analysis showed that the two ester groups of the diphenyl ester do not react independently. Furthermore, the reaction of the first ester group was of mixed second and third order, while the reaction of the second ester group contained only a second order term. The rate constants found were used to determine the Arrhenius activation parameters.

ChemInform Abstract: A Non-Catalyzed Ring-Opening Aminolysis Reaction of Sesquiterpene Lactones.

2010

Abstract Santonin (1) and other sesquiterpene lactones (6–10) react cleanly with pyrrolidine at room temperature to afford γ-hydroxyalkylamides, which by elimination with mesyl chloride in pyridine-benzene at 80°C give unsaturated alkylamides.

Torque rheometry investigation of model transreactions involving condensation polymers: I. Polyesters

2005

The chemical transformations taking place when poly(ethylene terephthalate) (PET) or poly(ethylene naphthalate) (PEN) are blended in the melt with different low molar mass substances containing hydroxyl, carboxyl, or amine functional groups have been investigated as models of the transreactions, undergone by the polyesters in reactive blending operations. The polyester molecular weight changes caused by the alcoholysis, acidolysis, aminolysis, and esterolysis reactions have been monitored by torque-rheometry, using a Brabender Plasticorder static mixer. The degradation of the polyesters by hydrolysis was also studied, under similar conditions, by the addition of a water-releasing substance …

Undecylenic acid: A tunable bio-based synthon for materials applications

2016

International audience; An undecylenic acid-based monoglyceride prepared from glycidol and undecylenic acid is used as suitable and tunable synthon for polymerization applications. Epoxidation and acrylation reactions lead to photopolymerizable monomers while transesterification with dimethyl carbonate, metathesis and aminolysis reactions provide access to polyhydroxyurethane-based materials. The successive intermediates were synthesized according to a green chemistry approach implicating solvent-less and catalyzed reactions, and were at each step fully characterized by infrared, 1H and 13C{1H} NMR spectroscopy, elemental analysis and mass spectrometry. Analyses of the resulting polymer mat…

A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis

2008

Macromolecules is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Communication to the Editor A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis Peter J. Roth, Daniel Kessler, Rudolf Zentel, and Patrick Theato Macromolecules, 2008, 41 (22), 8316-8319 • Publication Date (Web): 01 November 2008 Downloaded from http://pubs.acs.org on November 19, 2008

Formation of the Cationic [(2‐Aminoethenyl)carbine]iron Complexes by Treatment of (2‐Methoxyethenyl)carbene Complexes with Primary Amines:Synthesis a…

1997

Cationic (2-methoxyethenyl)methoxycarbene iron complexes 2, [Cp(CO)2Fe(C(OMe)CHCR(OMe))+][PF6−], are obtained by the addition of methanol to the corresponding (alkynyl)-methoxycarbene complexes 1, [Cp(CO)2Fe(C(OMe)CCR)+][PF6−]. Primary amines, H2NR', react with these 1,3-dimethoxy-substituted (alkenyl)carbene complexes, 2, through an addition/elimination process to yield cationic (2-aminoethenyl)methoxycarbene iron complexes, 3, [Cp(CO)2Fe(C(OMe)CHCR(NHR'))+][PF6−] in an isolated yield of 71–90%. The complexes 3a–c were characterized by X-ray structural analyses. Thus, previously isolated products, from the reaction, of the (alkynyl)methoxycarbene complexes 1a and 1c, with aniline at room t…

l-glutamine: a major substrate for tumor cells in vivo?

1987

From 65 human breast cancer xenografts investigated, a net glutamine uptake was found in 13 tumors (mean +/- SE: 15.7 +/- 4.5 nmol/g per min) whereas a net release (22.5 +/- 3.3 nmol/g per min) was observed in 40 tumors. In 12 tumors neither a significant net uptake nor a net release was obvious. There is experimental evidence that glutamine is taken up by cancer cells only at arterial concentrations greater than 0.5 mM. Another parameter determining glutamine utilization by tumor cells may be the tissue oxygenation. In hypoxic or anoxic tumor areas, glutamine oxidation is unlikely since oxygen is required for the reoxidation of coenzymes which are reduced in the course of this metabolic pa…

Role of Solvent on Nonenzymatic Peptide Bond Formation Mechanisms and Kinetic Isotope Effects

2013

Based on the hypothesis that similar mechanisms are involved in the peptide bond formation in aqueous solution and in the ribosome, the aminolysis of esters in aqueous solution has been the subject of numerous studies as the reference reaction for the catalyzed process. The mechanisms proposed in the literature have been explored in the present paper by hybrid QM/MM molecular dynamics simulations. The free energy profiles have been computed with the QM region of the system described at semiempirical AM1 level and by DFT within the M06-2X functional. According to the results, the formation of adduct zwitterion species is a preliminary step required for all possible mechanisms. Then, from dif…