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1.
Talanta ; 237: 122921, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34736658

RESUMO

Novel atmospheric pressure glow discharge (APGD) microplasma systems, sustained between a miniaturized flowing anode (FLA) or cathode (FLC) and a He jet, were investigated for the direct determination of Br and Cl, using optical emission spectrometry (OES). The impact of the most crucial operating parameters, i.e., the acid type and its concentration, the discharge current, the gas flow rate, and the sample flow rate, was studied for each of the proposed APGD-based systems. Under the optimized conditions, the analytical figures of merit were determined. The susceptibility to the matrix effects of both developed methods was verified as well. It was found that the mechanism of the analytes transport into the discharge likely relied on the cathode sputtering in the case of FLC-APGD and the formation of the volatile Br and Cl species for FLA-APGD. The DLs of Br and Cl were established to be relatively high, i.e., 0.15 and 1.5 mg L-1 for FLA-APGD and 2.1 and 18 mg L-1 for FLC-APGD. However, both studied methods turned out to be resistant to the presence of foreign ions in a sample, at relatively high concentrations. Hence, the proposed methods could be successfully applied for the determination of Br and Cl in water and juices samples and no major differences between the results obtained using the external standard calibration and the standard addition method were found.


Assuntos
Brometos , Cloretos , Pressão Atmosférica , Análise Espectral , Água
2.
J Environ Sci (China) ; 110: 111-118, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34593181

RESUMO

To ensure the safety of drinking water, ozone (O3) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br-). Considering the risk of bromate (BrO3-) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H2O2) and ammonia (NH3) on BrO3- formation during ozonation process were compared. The addition of H2O2 effectively inhibited BrO3- formation at an initial Br- concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H2O2/O3 was 0.25 and > 0.5, respectively. The UV254 and total organic carbon (TOC) also decreased after adding H2O2, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H2O2. To control the formation of both BrO3- and THMs, a relatively large dose of O3 and a high ratio of H2O2/O3were generally needed. NH3 addition inhibited BrO3- formation when the background ammonia nitrogen (NH3N) concentration was low. There was no significant correlation between BrO3- inhibition efficiency and NH3 dose, and a small amount of NH3N (0.2 mg/L) could obviously inhibit BrO3- formation. The oxidation of NOM seemed unaffected by NH3 addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH3. Considering the formation of BrO3- and THMs, the optimal dose of NH3 was suggested to be 0.5 mg/L.


Assuntos
Ozônio , Poluentes Químicos da Água , Purificação da Água , Amônia , Bromatos , Brometos , Peróxido de Hidrogênio , Trialometanos , Água , Poluentes Químicos da Água/análise
3.
Anal Chim Acta ; 1181: 338850, 2021 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-34556215

RESUMO

Latent fingerprints (LFPs) are one of the most important forms of evidence in crime scenes due to the uniqueness and permanence of the friction ridges in fingerprints. Therefore, an efficient method to detect LFPs is crucial in forensic science. However, there remain several challenges with traditional detection strategies including low sensitivity, low contrast, high background, and complicated processing steps. In order to overcome these drawbacks, we present an approach for developing latent fingerprints using stabilized CsPbBr3 perovskite nanocrystals (NCs) as solid-state nanopowders. We demonstrate the superior optical stability of CsPbBr3 NCs with respect to absorption, photoluminescence (PL), and fluorescence lifetime. We then used these highly stable, fluorescent CsPbBr3 NCs as a powder dusting material to develop LFPs on diverse surfaces. The stable optical properties and hydrophobic surface of the CsPbBr3 NC nanopowder permitted high resolution images from which unique features of friction ridge arrangements with first, second, and third-level LFP details can be obtained within minutes.


Assuntos
Brometos , Nanopartículas , Compostos de Cálcio , Césio , Chumbo , Óxidos , Titânio
4.
Int J Mol Sci ; 22(18)2021 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-34576028

RESUMO

Lung cancer is one of the most common cancers and the leading cause of death in humans worldwide. Non-small-cell lung cancer (NSCLC) accounts for approximately 85% of lung cancer cases and is often diagnosed at a late stage. Among patients with NSCLC, 50% die within 1 year after diagnosis. Even with clinical intervention, the 5-year survival rate is only approximately 20%. Therefore, the development of an advanced therapeutic strategy or novel agent is urgently required for treating NSCLC. Berberine exerts therapeutic activity toward NSCLC; therefore, its activity as an antitumor agent needs to be explored further. In this study, three terpenylated-bromide derivatives of berberrubine were synthesized and their anti-NSCLC activities were evaluated. Each derivative had higher anti-NSCLCs activity than berberrubine and berberine. Among them, 9-O-gernylberberrubine bromide (B4) and 9-O-farnesylberberrubine bromide (B5) showed greater growth inhibition, cell-cycle regulation, in vitro tumorigenesis suppression, and tumor migration reduction. In addition, some degree of apoptosis and autophagic flux blocking was noted in the cells under B4 and B5 treatments. Our study demonstrates that the berberrubine derivatives, B4 and B5, exhibit impressive anti-NSCLC activities and have potential for use as chemotherapeutic agents against NSCLC.


Assuntos
Berberina/análogos & derivados , Carcinoma Pulmonar de Células não Pequenas/tratamento farmacológico , Movimento Celular/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Células A549 , Antineoplásicos/farmacologia , Apoptose/efeitos dos fármacos , Berberina/síntese química , Berberina/química , Berberina/farmacologia , Brometos/química , Carcinogênese/efeitos dos fármacos , Carcinoma Pulmonar de Células não Pequenas/patologia , Humanos , Terpenos/síntese química , Terpenos/farmacologia
5.
J Occup Health ; 63(1): e12274, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34587337

RESUMO

OBJECTIVES: In this study, we aimed to establish a method for quantifying bromide ions (Br- ) in blood and urine using gas chromatograph-mass spectrometer (GC-MS) equipped with a headspace sampler, for biological monitoring of workers exposed to methyl bromide. METHODS: Samples were mixed with dimethyl sulfate, and Br- ions were detected using GC-MS with a headspace sampler. The validity of the proposed method was evaluated based on most of the US FDA guidance. The values obtained were compared with reference values by analysis using SeronormTM Trace Elements Whole Blood L-1 RUO. RESULTS: The calibration curve showed good linearity in the Br- concentration range of 0.1-20.0 mg/L, and the coefficient of determination R2 value was >.999. Intraday and interday accuracy values were 99.3%-103.1% and 97.4%-101.8%, respectively. The measured and reference values of Seronorm were concordant. Herein, eight urine and serum samples of workers were analyzed; the samples' Br- concentrations were known. The correlation coefficients of urine and serum samples were 0.97 and 0.96, respectively, and results were consistent. CONCLUSIONS: This study established a simple and rapid method for the determination of Br- concentration in biological samples using GC-MS with a headspace sampler. Moreover, it can be used for biological monitoring of occupational exposure to methyl bromide and for the determination of Br- concentration in a wide range of biological samples.


Assuntos
Monitoramento Biológico/métodos , Brometos/sangue , Brometos/urina , Cromatografia Gasosa-Espectrometria de Massas/métodos , Humanos , Hidrocarbonetos Bromados/análise , Exposição Ocupacional/análise , Valores de Referência , Reprodutibilidade dos Testes
6.
Int J Mol Sci ; 22(17)2021 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-34502193

RESUMO

Redox flow batteries (RFB) are one of the most interesting technologies in the field of energy storage, since they allow the decoupling of power and capacity. Zinc-bromine flow batteries (ZBFB) are a type of hybrid RFB, as the capacity depends on the effective area of the negative electrode (anode), on which metallic zinc is deposited during the charging process. Gaseous bromine is generated at the positive electrode (cathode) during the charging process, so the use of bromine complexing agents (BCA) is very important. These BCAs are quaternary amines capable of complexation with bromine and generating an organic phase, immiscible with the aqueous electrolyte. One of the most commonly used BCAs in RFB technology is 4-methylethylmorpholinium bromide (MEM-Br). In this work, an alternative quaternary amine 4-methylpropylmorpholinium bromide (MPM-Br) was studied. MPM-Br was integrated into the electrolyte, and 200 charge-discharge cycles were performed on the resulting ZBFBs. The obtained results were compared with those when MEM-Br was used, and it was observed that the electrolyte with MPM-Br displays a higher resistance in voltage and higher energy efficiency, making it a promising alternative to MEM-Br.


Assuntos
Brometos/química , Fontes de Energia Elétrica , Eletrodos , Hidrocarbonetos Bromados/química , Zinco/química , Oxirredução
7.
J Org Chem ; 86(18): 13153-13159, 2021 09 17.
Artigo em Inglês | MEDLINE | ID: mdl-34476948

RESUMO

Herein we describe an efficient construction of HCF2Se and HCF2S groups by tandem substitutions between alkyl bromides and a reagent system consisting of MSeCN (or MSCN) and Ph3P+CF2H Br-. The tandem process occurs via the first nucleophilic substitution of alkyl bromides by -SeCN (or -SCN) and the subsequent nucleophilic difluoromethylation.


Assuntos
Brometos , Indicadores e Reagentes
8.
Water Res ; 204: 117569, 2021 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-34461497

RESUMO

The UV/monochloramine (UV/NH2Cl) process has attracted increasing attention in water treatment, in which hydroxyl radicals (HO•), reactive chlorine species (RCS) and reactive nitrogen species (RNS) are produced. This study investigated the effects of water matrices including halides, natural organic matter (NOM), alkalinity and pH, on the degradation kinetic of a variety of micropollutants and radical chemistry in the UV/NH2Cl process. The presence of chloride blunted HO• and Cl• impacts, but enhanced Cl2•- effect on micropollutants reactive toward Cl2•-. The presence of 30 µM bromide led to an 82% decrease in the specific pseudo-first-order rate constants (k') by HO• (kHO•'), and significantly diminished RCS efficacy. Reactive bromine species (RBS) were formed in the presence of bromide, while the contribution could not compensate for the decrease of HO• and RCS due to their lower reactivity toward micropollutants. Iodide rapidly transformed to HOI via reacting with NH2Cl, which resulted in a 59% decrease of kHO•' and 12% ∼ 100% decreases of k' by reactive halogen species (RHS) and RNS (kRHS + RNS') for most micropollutants. Nevertheless, k' of phenolic compounds, such as paracetamol, bisphenol A and salbutamol, increased in the presence of iodide by 78%, 360% and 130%, respectively, due to the roles of HOI and reactive iodine species (RIS). Bicarbonate decreased the contributions of HO• and RCS, but enhanced that of CO3•- for micropollutants reactive toward CO3•-. The presence of 1 mg/L NOM scavenged over half the amount of HO•, and also consumed RCS and RNS, resulting in significantly decreased removal of micropollutants. High pH value witnessed enhanced degradation for those micropollutants reactive toward RCS and RNS through deprotonation. The degradation of most micropollutants was inhibited in real drinking water and in the coexistence of halides. This study provides a better understanding of radical chemistry in the UV/NH2Cl process under a practical water treatment condition.


Assuntos
Água Potável , Osteosclerose , Poluentes Químicos da Água , Purificação da Água , Brometos , Cloretos , Cloro , Humanos , Cinética , Oxirredução , Raios Ultravioleta
9.
Int J Mol Sci ; 22(16)2021 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-34445690

RESUMO

Platinum coordination complexes have found wide applications as chemotherapeutic anticancer drugs in synchronous combination with radiation (chemoradiation) as well as precursors in focused electron beam induced deposition (FEBID) for nano-scale fabrication. In both applications, low-energy electrons (LEE) play an important role with regard to the fragmentation pathways. In the former case, the high-energy radiation applied creates an abundance of reactive photo- and secondary electrons that determine the reaction paths of the respective radiation sensitizers. In the latter case, low-energy secondary electrons determine the deposition chemistry. In this contribution, we present a combined experimental and theoretical study on the role of LEE interactions in the fragmentation of the Pt(II) coordination compound cis-PtBr2(CO)2. We discuss our results in conjunction with the widely used cancer therapeutic Pt(II) coordination compound cis-Pt(NH3)2Cl2 (cisplatin) and the carbonyl analog Pt(CO)2Cl2, and we show that efficient CO loss through dissociative electron attachment dominates the reactivity of these carbonyl complexes with low-energy electrons, while halogen loss through DEA dominates the reactivity of cis-Pt(NH3)2Cl2.


Assuntos
Brometos/química , Complexos de Coordenação/química , Compostos de Platina/química , Antineoplásicos/química , Brometos/farmacologia , Cisplatino/farmacologia , Elétrons , Platina , Compostos de Platina/farmacologia
10.
J Org Chem ; 86(18): 12772-12782, 2021 09 17.
Artigo em Inglês | MEDLINE | ID: mdl-34459192

RESUMO

Herein, we describe a convenient general protocol for monofluoroalkenylation reactions of alkyl bromides involving cooperative visible-light photoredox catalysis and halogen abstraction. Mechanistic experiments showed that the products were generated by selective cross-coupling of aliphatic radicals with fluoroalkenyl radicals. Silyl radical-mediated halogen abstraction enabled the protocol to be used for the monofluoroalkenylation of a broad range of alkyl and heteroaryl halides. The protocol could be carried out on a gram scale and was applied to cholesterol, indicating its utility for late-stage monofluoroalkenylation reactions.


Assuntos
Brometos , Halogênios , Catálise , Luz
11.
Nat Commun ; 12(1): 4924, 2021 08 13.
Artigo em Inglês | MEDLINE | ID: mdl-34389709

RESUMO

C-Glycosyl peptides/proteins are metabolically stable mimics of the native glycopeptides/proteins bearing O/N-glycosidic linkages, and are thus of great therapeutical potential. Herein, we disclose a protocol for the syntheses of vinyl C-glycosyl amino acids and peptides, employing a nickel-catalyzed reductive hydroglycosylation reaction of alkyne derivatives of amino acids and peptides with common glycosyl bromides. It accommodates a wide scope of the coupling partners, including complex oligosaccharide and peptide substrates. The resultant vinyl C-glycosyl amino acids and peptides, which bear common O/N-protecting groups, are amenable to further transformations, including elongation of the peptide and saccharide chains.


Assuntos
Alcinos/química , Aminoácidos/química , Glicosídeos/química , Níquel/química , Peptídeos/química , Brometos/química , Sequência de Carboidratos , Catálise , Dissacarídeos/química , Glicopeptídeos/síntese química , Glicopeptídeos/química , Glicosídeos/síntese química , Glicosilação , Modelos Químicos , Estrutura Molecular , Monossacarídeos/química , Oxirredução
12.
Angew Chem Int Ed Engl ; 60(42): 22977-22982, 2021 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-34427992

RESUMO

We report a Ni-catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3-triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate-limiting single-electron-transfer process and is autocatalyzed by in-situ-generated ZnX2 . The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2 .


Assuntos
Alcenos/química , Brometos/química , Níquel/química , Compostos de Zinco/química , Compostos de Benzil/química , Catálise , Cinética
13.
Ind Health ; 59(4): 239-248, 2021 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-34261823

RESUMO

Previously, we reported that prenatal exposure to 1-bromopropane (1-BP) causes the accumulation of bromide (Br-) in the brain of rat pups. Here, we aimed to investigate the effects of Br- accumulation in rat pups prenatally exposed to 1-BP vapor. Dam rats were exposed to 1-BP (400 or 700 ppm; 1-BP group) by inhalation, or to NaBr (20 mM; Br- group) in drinking water during gestation days 1-20. We also analyzed pentylenetetrazole (PTZ, 60 mg/kg, ip)-induced behavioral changes in pups prenatally exposed to 1-BP or Br- on postnatal day (PND) 14. PTZ-induced epileptic convulsions were inhibited in both 1-BP (700 ppm) and Br- groups. The inhibition of neuronal excitability induced by Br- was evaluated electrophysiologically using the hippocampal slices obtained from PND14-16 pups. PTZ (2 mM) failed to induce epileptiform discharge in the presence of 1.2 mM Br- in the slices obtained from the control group. However, it induced epileptiform discharge following the removal of Br-, by perfusing artificial cerebrospinal fluid into the slices obtained from the Br- group. Our results indicate that Br- accumulates in the brain of neonatal rat pups prenatally exposed to 1-BP vapor suppressed neuronal excitability.


Assuntos
Brometos , Efeitos Tardios da Exposição Pré-Natal , Animais , Encéfalo , Feminino , Hidrocarbonetos Bromados , Gravidez , Efeitos Tardios da Exposição Pré-Natal/induzido quimicamente , Ratos , Ratos Wistar
14.
Chemistry ; 27(51): 12981-12986, 2021 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-34233043

RESUMO

High-throughput experimentation (HTE) methods are central to modern medicinal chemistry. While many HTE approaches to C-N and Csp2 -Csp2 bonds are available, options for Csp2 -Csp3 bonds are limited. We report here how the adaptation of nickel-catalyzed cross-electrophile coupling of aryl bromides with alkyl halides to HTE is enabled by AbbVie ChemBeads technology. By using this approach, we were able to quickly map out the reactivity space at a global level with a challenging array of 3×222 micromolar reactions. The observed hit rate (56 %) is competitive with other often-used HTE reactions and the results are scalable. A key to this level of success was the finding that bipyridine 6-carboxamidine (BpyCam), a ligand that had not previously been shown to be optimal in any reaction, is as general as the best-known ligands with complementary reactivity. Such "cryptic" catalysts may be common and modern HTE methods should facilitate the process of finding these catalysts.


Assuntos
Compostos Heterocíclicos , Níquel , Brometos , Catálise , Ligantes
15.
Sci Total Environ ; 795: 148786, 2021 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-34229237

RESUMO

Bromate, a toxic by-product of bromide-containing drinking water after disinfecting with ozone, has attracted much attention in the past two decades. Traditional methods to activate zero-valent metals for reducing bromate are to eliminate their surface oxide layer by acid washing. In this work, for the first time, zero-valent Al (ZVAl) was surface treated by the following procedures including soaking, soaking and freeze-drying, soaking and heat-treating, and γ-Al2O3 covering Al particle surfaces (GCAP). It was found that all of above surface treated ZVAls have an obvious high efficiency for bromate reduction relative to pristine ZVAl. The bromate reduction rate is GCAP > soaking Al > freeze-drying Al > soaking and heat-treating Al > pristine Al, and using GCAP just 30 min is taken to completely reduce bromate to bromide in neutral solution. Mechanism analyses revealed that Al surface treating or covered by fine γ-Al2O3 phase can promote the hydration and breakage of Al surface passive oxide layer, resulting in a fast contact of inner Al with outside ions, leading to a high reduction rate of bromate in neutral solution. XPS analyses indicated that there are no bromate or bromide ions adsorbed on Al particle surfaces, implying that there is a high direct donating efficiency of electrons from inner Al to bromate ions in solution. Furthermore, GCAP has a good reusability and >90% bromate can be reduced even it was reused up to 4 cycles.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Alumínio , Bromatos , Brometos , Oxirredução
16.
Sci Total Environ ; 795: 148772, 2021 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-34247079

RESUMO

Due to the negative impact of climate change and anthropogenic activities, bromide intrusion into algae-impacted freshwater becomes a new challenge for safe drinking water supply worldwide, as bromide and algal organic matter are important disinfection byproduct (DBP) precursors. However, the influences of this phenomenon on algal precursor dynamic and their derived DBPs have to date received little attention. This study examined the effects of bromide intrusion on algal intra- (IOM) and extra-cellular (EOM) precursors during the growth of two freshwater algae Chlorella sp. and Microcystis aeruginosa. Both algae were well-adapted to Br-intrusion, and no significant effect on their growth and their IOM and EOM precursor characteristics was statistically found (p > 0.05). Notwithstanding, this phenomenon apparently added bromide ions into the algal-EOM solution, which resulted in a linear uptake of bromide by IOM. Under Br-intrusion from 0-4 mg/L (Br0-Br4), 15-60% (on average) of the initial bromide additions remained in the algal EOM. By contrast, only an average of ~1.5-2.4% of the additional bromide was taken up by the IOM, resulting in an elevation of brominated DBPs (Br-DBPs) upon chlorination, especially for those samples collected in the late exponential and declined growth phases. When Br0 shifted to Br4, the %Br-DBP yields from both IOM and EOM increased by more than 75%, with a corresponding increasing the total DBP yield of ~30%. The toxic potencies of all chlorinated Br-containing IOM/EOM were thus magnified, by over one order magnitude greater than the non-Br IOM/EOM at Br0. These results are highly significant for understanding the potential risks of Br-intrusion and algal blooming in raw water quality prior to chlorination.


Assuntos
Chlorella , Desinfetantes , Microcystis , Poluentes Químicos da Água , Purificação da Água , Brometos , Desinfetantes/toxicidade , Desinfecção , Halogenação , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
17.
J Chromatogr A ; 1652: 462370, 2021 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-34246961

RESUMO

A fast and automated separation and quantification method for bromide and the artificial nucleoside 5-bromo-2'-deoxyuridine (5-BrdU) via hyphenation of ion exchange chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS) is presented. The analysis of these two species is relevant to monitor the transfer of electrons along metal-mediated DNA base pairs. Charge transfer in DNA is of high interest for the implementation in nanotechnological applications like molecular wires. 5-BrdU as part of the DNA sequence releases bromide upon one electron reduction after efficient electron transfer along the DNA. The concentrations of 5-BrdU and bromide in enzymatically digested DNA samples can therefore be used as a marker for the efficiency of electron transfer along the DNA helix. A large number of samples was analyzed using an automated IC system. This platform enables time-efficient external calibration by inline dilution of a stock solution. Due to the fast separation of the two bromine species in less than 90 s, the developed method is suitable for screening applications with a multitude of samples. Despite the isobaric interferences and a low degree of ionization for bromine detection via ICP-MS the method has a limit of detection (LOD) of 30 ng/L which is approximately an order of magnitude lower than a comparable method using reversed phase high performance liquid chromatography (RP-HPLC) and ICP-MS.


Assuntos
Brometos , Bromo , Bromodesoxiuridina , Técnicas de Química Analítica , Espectrometria de Massas , Brometos/análise , Bromo/química , Bromodesoxiuridina/análise , Técnicas de Química Analítica/métodos , Cromatografia por Troca Iônica , DNA/química
18.
J Org Chem ; 86(15): 10829-10837, 2021 08 06.
Artigo em Inglês | MEDLINE | ID: mdl-34240599

RESUMO

Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.


Assuntos
Brometos , Cloretos , Catálise , Ligantes , Sulfetos
19.
J Org Chem ; 86(15): 10914-10920, 2021 08 06.
Artigo em Inglês | MEDLINE | ID: mdl-34260227

RESUMO

Metallaphotoredox-catalyzed C-S cross-coupling between heteroaryl bromides and α-thioacetic acids to form biaryl thioethers is described herein. This transformation allows for cross-coupling between building blocks containing reactive functional groups, nitrogen heterocycles, and pharmaceutically relevant scaffolds. Mechanistic experiments indicate a unique means by which this C-S cross-coupling occurs.


Assuntos
Brometos , Sulfetos , Catálise , Nitrogênio
20.
J Org Chem ; 86(15): 9938-9944, 2021 08 06.
Artigo em Inglês | MEDLINE | ID: mdl-34269577

RESUMO

The synthesis of aryl selenonic acids was achieved from diverse aryl bromides via a one-pot method involving metalation, selenation, and oxidation with hydrogen peroxide followed by ion exchange to afford the pure products in 77-90% yield. An o-hydroxymethyl derivative was found to dehydrate readily, affording the first example of a cyclic selenonic ester, while two minor byproducts were isolated and shown by X-ray crystallography to be mixed salts of aryl selenonic acids with either the corresponding aryl seleninic or selenious acid.


Assuntos
Brometos , Sais , Oxirredução
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