Chemoselektive γ‐Oxidation von β,γ‐ungesattigten Amiden mit TEMPO
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ABSTRACT:
SUBMITTER: Heindl S
PROVIDER: S-EPMC10946935 | biostudies-literature | 2021 Jul
REPOSITORIES: biostudies-literature
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Project description:A chemoselective and robust protocol for the γ-oxidation of β,γ-unsaturated amides is reported. In this method, electrophilic amide activation, in a rare application to unsaturated amides, enables a regioselective reaction with TEMPO resulting in the title products. Radical cyclisation reactions and oxidation of the synthesised products highlight the synthetic utility of the products obtained.
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Project description:Aldehydes are important synthons for DNA-encoded library (DEL) construction, but the development of a DNA-compatible method for the oxidation of alcohols to aldehydes remains a significant challenge in the field of DEL chemistry. We report that a copper/TEMPO catalyst system enables the solution-phase DNA-compatible oxidation of DNA-linked primary activated alcohols to aldehydes. The semiaqueous, room-temperature reaction conditions afford oxidation of benzylic, heterobenzylic, and allylic alcohols in high yield, with DNA compatibility verified by mass spectrometry, qPCR, Sanger sequencing, and ligation assays. Subsequent transformations of the resulting aldehydes demonstrate the potential of this method for robust library diversification.
| S-EPMC10831869 | biostudies-literature
Project description:Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols.
| S-EPMC3834274 | biostudies-literature
Project description:Primary objectives: Primäres Studienziel der Phase IDefinition der empfohlenen Dosis von Capecitabin und Oxaliplatin bei gleichzeitiger Therapie mit Bevacizumab und Imatinib.
Primäres Studienziel der Phase IIMachbarkeit und Verträglichkeit der in der Phase I ermittelten Dosis der Kombination aus XELOX mit Bevacizumab und Imatinib anhand der Bestimmung der Sicherheit und der Nebenwirkungen und Toxizitäten der Kombinationstherapie.
Primary endpoints: Phase I
Definition der empfohlenen Dosis von Capecitabin und Oxaliplatin bei gleichzeitiger Therapie mit Imatinib und Bevacizumab.
Phase II
Bestimmung der Sicherheit und der Nebenwirkungen und Toxizitäten der Kombinationstherapie mit Capecitabin, Oxaliplatin, Imatinib und Bevacizumab
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Project description:The native cellulose, through TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation, can be converted into individual fibers. It has been observed that oxidized fibers disperse completely and individually in water. It is believed that electrostatic repulsive forces might be responsible for such observations. In order to study the TEMPO-oxidation of cellulose molecules, we used Density Functional Theory (DFT) calculations and Flory-Huggins theory combined with molecular dynamics (MD). The surface electrostatic potential in native cellulose and TEMPO-oxidized cellulose were calculated using DFT calculations. We found that TEMPO-oxidized cellulose accommodates a threefold screw conformation where the negatively charged (-COO-) functional groups are pointed away from the surface in all spatial directions. This spatial orientation causes that TEMPO-oxidized cellulose molecules repulse each other due to strong negatively charged surface. At the same time, the spatial orientation increases the hydrophilicity in TEMPO-oxidized cellulose molecules. These observations explain the improved dispersion in water and separability of TEMPO-oxidized cellulose molecules. We obtained large and positive Flory-Huggins interaction parameters for TEMPO-oxidized cellulose molecules indicating their higher dispersion once in water.
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Project description:A protocol for the oxidation of alcohols to aldehydes and ketones employing an electrochemical aminoxyl-mediated reaction is presented. The approach employs a catalytic amount of the radical and the use of a base is not required. It is performed using readily available electrodes in a commercially available electrochemistry apparatus and does not require a reference electrode. The methodology is applicable to a range of structurally and electronically diverse substrates, including the oxidation of primary alcohols to aldehydes rather than the more commonly formed carboxylic acids.
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Project description:This work reports an aqueous dye-sensitized photoelectrochemical cell (DSPEC) capable of oxidizing glycerol (an archetypical biobased compound) coupled with H2 production. We employed a mesoporous TiO2 photoanode sensitized with the high potential thienopyrroledione-based dye AP11, encased in an acetonitrile-based redox-gel that protects the photoanode from degradation by aqueous electrolytes. The use of the gel creates a biphasic system with an interface at the organic (gel) electrode and aqueous anolyte. Embedded in the acetonitrile gel is 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), acting as both a redox-mediator and a catalyst for oxidative transformations. Upon oxidation of TEMPO by the photoexcited dye, the in situ generated TEMPO+ shuttles through the gel to the acetonitrile-aqueous interface, where it acts as an oxidant for the selective conversion of glycerol to glyceraldehyde. The introduction of the redox-gel layer affords a 10-fold increase in the conversion of glycerol compared to the purely aqueous system. Our redox-gel protected photoanode yielded a stable photocurrent over 48 hours of continuous operation, demonstrating that this DSPEC is compatible with alkaline aqueous reactions.
| S-EPMC9401026 | biostudies-literature
Project description:Enamine and imine represent two of the most common reaction intermediates in syntheses, and the imine intermediates containing α-hydrogen often exhibit the similar reactivity to enamines due to their rapid tautomerization to enamine tautomers. Herein, we report that the minor structural difference between the enamine and the enamine tautomer derived from imine tautomerization results in the different chemo- and regioselectivity in the reaction of cyclohexanones, amines and TEMPO: the reaction of primary amines furnishes the formal oxygen 1,2-migration product, α-amino-enones, while the reaction of secondary amines under similar conditions generates exclusively arylamines via consecutive dehydrogenation on the cyclohexyl rings. The 18O-labeling experiment for α-amino-enone formation revealed that TEMPO served as oxygen transfer reagent. Experimental and computational studies of reaction mechanisms revealed that the difference in chemo- and regioselectivity could be ascribed to the flexible imine-enamine tautomerization of the imine intermediate containing an α-hydrogen.
| S-EPMC6258700 | biostudies-literature
Project description:Combinations of homogeneous Cu salts and TEMPO have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2'-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols.
| S-EPMC3925889 | biostudies-literature
Project description:A new metal-free protocol for promoting oxidation of amines in aqueous-organic medium was developed. NaIO4 and TEMPO as the catalyst emerged as the most efficient and selective system for oxidation of differently substituted benzyl amines to the corresponding benzaldehydes without overoxidation. Unsymmetrical secondary amines underwent selective oxidation only at the benzylic position thus realising an oxidative deprotection of a benzylic group with an easy amine recovery.
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