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1.
Nano Lett ; 24(5): 1635-1641, 2024 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-38277778

RESUMEN

We present an on-chip filter with a broad tailorable working wavelength and a single-mode operation. This is realized through the application of topological photonic crystal nanobeam filters employing synthesis parameter dimensions. By introducing the translation of air holes as a new synthetic parameter dimension, we obtained nanobeams with tunable Zak phases. Leveraging the bulk-edge correspondence, we identify the existence of topological cavity modes and establish a correlation between the cavity's interface morphology and working wavelength. Through experiments, we demonstrate filters with adjustable filtering wavelengths ranging from 1301 to 1570 nm. Our work illustrates the use of the synthetic translation dimension in the design of on-chip filters, and it holds potential for applications in other devices such as microcavities.

2.
J Org Chem ; 89(1): 687-691, 2024 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-38101330

RESUMEN

An iodoform-promoted functionalization of ether with secondary sulfonyl amides under visible-light irradiation was developed toward synthesis of hemiaminal skeleton with good to excellent isolated yields. The characterization of the isolated ether and iodoform complex revealed regioselective hydrogen atom transfer to initiate carbon radical formation and enabled the amination reaction with the sulfonamide.

3.
Antonie Van Leeuwenhoek ; 117(1): 112, 2024 Aug 12.
Artículo en Inglés | MEDLINE | ID: mdl-39133351

RESUMEN

A Gram-stain-negative, light khaki, strictly aerobic, rod-shaped, motile via multiple flagella, and catalase- and oxidase-positive bacterium, designated as SSM4.3T, was isolated from the seaweed of Gouqi Island in the East China Sea. The novel isolate grows at 0-5.0% NaCl concentrations (w/v) (optimum 1%), pH 5.0-9.0 (optimum pH 7.0), and 15-37 °C (optimum 30 °C). The 16S rRNA gene sequences-based phylogeny indicates that the novel marine isolate belongs to the family Rhizobiaceae and that it shared the greatest sequence similarity (98.9%) with Peteryoungia rhizophila CGMCC 1.15691T. This classification was also supported by phylogenetic analysis using core genes. The predominant fatty acids (≥ 10%) of the strain were identified as C18:1 ω7c/C18:1 ω6c. Q-10 was identified as the major isoprenoid quinone, with trace levels of Q-9 present. The major polar lipids were identified as diphosphatidylglycerol, phosphatidylethanolamine and phosphatidylglycerol. The complete genome size of strain SSM4.3T is 4.39 Mb with a DNA G+C content of 61.3%. The average nucleotide identity, digital DNA-DNA hybridization, and average amino acid identity values between the genomes of strain SSM4.3T and its closely related representatives were 74.80-86.93%, 20.00-32.30%, and 70.30-91.52%, respectively. Phylogenetic analysis, grounded on the core genes, reveals the evolutionary relationship between SSM4.3T and other Peteryoungia strains. Pan-genomics analysis of 8 previously classified Peteryoungia species and SSM4.3T revealed their unique genetic features and functions. Overall, strain SSM4.3T was considered to be a new species of the Peteryoungia genus; the name Peteryoungia algae sp. nov. has been proposed, with type strain SSM4.3T (= LMG 32561 = MCCC 1K07170).


Asunto(s)
Composición de Base , ADN Bacteriano , Ácidos Grasos , Filogenia , ARN Ribosómico 16S , Algas Marinas , China , ARN Ribosómico 16S/genética , Algas Marinas/microbiología , ADN Bacteriano/genética , Ácidos Grasos/análisis , Ácidos Grasos/química , Técnicas de Tipificación Bacteriana , Genoma Bacteriano , Análisis de Secuencia de ADN , Islas , Hibridación de Ácido Nucleico
4.
Curr Microbiol ; 81(9): 283, 2024 Jul 27.
Artículo en Inglés | MEDLINE | ID: mdl-39066927

RESUMEN

A novel bacterium designated as SSA5.23T was isolated from seawater. Cells of SSA5.23T are Gram-stain-negative, short, rod-shaped, and exhibit motility via numerous peritrichous flagella. The strain could grow at temperatures ranging from 15 to 35 °C (optimum at 25 °C), in a salinity range of 0-5.0% (w/v) NaCl, and within a pH range of 6.0-9.0 (optimum at pH 7.0). The predominant cellular fatty acid of SSA5.23T was C18:1 ω7c/C18:1 ω6c, and the major respiratory quinones were Q-9 and Q-10. Diphosphatidylglycerol, phosphatidylethanolamine, and phosphatidylglycerol were identified as the primary polar lipids. The complete genome (5.47 Mb) of SSA5.23T comprises of a circular chromosome of 3.64 Mb and three plasmids, specifically sized at 59.73 kb, 227.82 kb, and 1.54 Mb, respectively. Certain genes located on the plasmids play roles in denitrification, oxidative stress resistance, and osmotic tolerance, which likely contribute to the adaptability of this strain in marine conditions. Core-proteome average amino acid identity analysis effectively identified the strain's affiliation with the genus Affinirhizobium, showing the highest value (89.9%) with Affinirhizobium pseudoryzae DSM 19479T. This classification was further supported by the phylogenetic analysis of concatenated alignment of 170 single-copy orthologous proteins. When compared to related reference strains, SSA5.23T displayed an average nucleotide identity ranging from 74.9 to 80.3% and digital DNA-DNA hybridization values ranging from 19.9 to 23.9%. Our findings confirmed that strain SSA5.23T represents a novel species of the genus Affinirhizobium, for which the name Affinirhizobium gouqiense sp. nov. (type strain SSA5.23T = LMG 32560T = MCCC 1K07165T) was suggested.


Asunto(s)
ADN Bacteriano , Ácidos Grasos , Genoma Bacteriano , Filogenia , Agua de Mar , Agua de Mar/microbiología , China , Ácidos Grasos/análisis , ADN Bacteriano/genética , Rhizobium/genética , Rhizobium/clasificación , Rhizobium/aislamiento & purificación , Composición de Base , Técnicas de Tipificación Bacteriana , ARN Ribosómico 16S/genética , Análisis de Secuencia de ADN , Islas , Genómica
5.
Zhongguo Zhong Yao Za Zhi ; 49(12): 3204-3211, 2024 Jun.
Artículo en Zh | MEDLINE | ID: mdl-39041081

RESUMEN

Ursolic acid has gradually attracted much attention due to its unique pharmacological activities and valuable market value in recent years. Currently, ursolic acid is mostly extracted from loquat leaves, but the plant extraction method has low yield and high cost, and chemical synthesis is not readily available, so the biosynthesis method provides a new source for ursolic acid. α-amyrin acts as the main precursor for the synthesis of ursolic acid, and its yield is positively correlated with ursolic acid yield. Oxidosqualene cyclase(OSC) belongs to a multigene family which can catalyze the common precursor 2,3-oxidosqualene to generate different types of triterpene backbones, and plays a decisive role in the synthesis of triterpenoids. However, there are fewer reported key genes catalyzing the synthesis of α-amyrin in medicinal plants, and the yield and proportion of α-amyrin in the catalyzed products have always been a focus of research. In this study, ItOSC2, MdOSC1, AaOSC2 and CrAS, four enzymes capable of catalyzing the production of α-amyrin from 2,3-oxidosqualene, were cloned from Iris tectorum, Malus domestica, Artemisia annua and Catharanthus roseus, subject to sequence alignment and phylogenetic tree analyses, and transformed into Saccharomyces cerevisiae as plasmids. After 7 days of fermentation, the yield and proportions of α-amyrin, ß-amyrin and ergosterol were measured. Finally, AaOSC2 with the best ability to catalyze the generation of α-amyrin was filtered out, providing a key gene element for the later construction of engineered yeast strains with high production of α-amyrin and ursolic acid.


Asunto(s)
Transferasas Intramoleculares , Ácido Oleanólico , Transferasas Intramoleculares/genética , Transferasas Intramoleculares/metabolismo , Ácido Oleanólico/análogos & derivados , Ácido Oleanólico/metabolismo , Ácido Oleanólico/química , Ácido Oleanólico/biosíntesis , Clonación Molecular , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Triterpenos/metabolismo , Triterpenos/química , Saccharomyces cerevisiae/genética , Saccharomyces cerevisiae/enzimología , Saccharomyces cerevisiae/metabolismo , Filogenia , Triterpenos Pentacíclicos
6.
Small ; 19(24): e2207817, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-36919945

RESUMEN

Both the uncoordinated Pb2+ and excess PbI2 in perovskite film will create defects and perturb carrier collection, thus leading to the open-circuit voltage (VOC ) loss and inducing rapid performance degradation of perovskite solar cells (PSCs). Herein, an additive of 3-aminothiophene-2-carboxamide (3-AzTca) that contains amide and amino and features a large molecular size is introduced to improve the quality of perovskite film. The interplay of size effect and adequate bonding strength between 3-AzTca and uncoordinated Pb2+ regulates the mineralization of PbI2 and generates low-dimensional PbI2 phase, thereby boosting the crystallization of perovskite. The decreased defect states result in suppressed nonradiative recombination and reduced VOC loss. The power conversion efficiency (PCE) of modified PSC is improved to 22.79% with a high VOC of 1.22 V. Moreover, the decomposition of PbI2 and perovskite films is also retarded, yielding enhanced device stability. This study provides an effective method to minimize the concentration of uncoordinated Pb2+ and improve the PCE and stability of PSCs.

7.
Chemistry ; 29(51): e202301633, 2023 Sep 12.
Artículo en Inglés | MEDLINE | ID: mdl-37365999

RESUMEN

Described herein is a visible-light photoredox-catalyzed regioselective 1,4-hydroalkylation of 1,3-enynes. Various of di- and tri-substituent allenes were really accessible under the present reaction conditions. The visible-light photoredox activation of the carbon nucleophile to generate its radical species, allowing the addition with un-activated enynes. The synthetic utility for the present protocol was demonstrated by a large-scale reaction, as well as the derivatization of the allene product.

8.
Brain Behav Immun ; 109: 23-36, 2023 03.
Artículo en Inglés | MEDLINE | ID: mdl-36581303

RESUMEN

Synapse loss in medial prefrontal cortex (mPFC) has been implicated in stress-related mood disorders, such as depression. However, the exact effect of synapse elimination in the depression and how it is triggered are largely unknown. Through repeated longitudinal imaging of mPFC in the living brain, we found both presynaptic and postsynaptic components were declined, together with the impairment of synapse remodeling and cross-synaptic signal transmission in the mPFC during chronic stress. Meanwhile, chronic stress also induced excessive microglia phagocytosis, leading to engulfment of excitatory synapses. Further investigation revealed that the elevated complement C3 during the stress acted as the tag of synapses to be eliminated by microglia. Besides, chronic stress induced a reduction of the connectivity between the mPFC and neighbor regions. C3 knockout mice displayed significant reduction of synaptic pruning and alleviation of disrupted functional connectivity in mPFC, resulting in more resilience to chronic stress. These results indicate that complement-mediated excessive microglia phagocytosis in adulthood induces synaptic dysfunction and cortical hypo-connectivity, leading to stress-related behavioral abnormality.


Asunto(s)
Microglía , Derrota Social , Ratones , Animales , Sinapsis , Ratones Noqueados , Plasticidad Neuronal
9.
J Org Chem ; 88(22): 15969-15974, 2023 Nov 17.
Artículo en Inglés | MEDLINE | ID: mdl-37903348

RESUMEN

Described herein is a photoinduced copper-catalyzed 1,2-difunctionalization of 1,3-dienes. The selenium atom radical was generated by the visible light irradiation of diselenides, triggering radical addition with 1,3-dienes to form allyl radical intermediate. Subsequent rapid Z/E isomerization allowed for thermodynamically favorable intermediate formation and enabled copper catalyzed stereoselective functionalization with various nucleophiles.

10.
J Org Chem ; 88(23): 16639-16643, 2023 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-37976542

RESUMEN

A radical hydroalkylative cyclization approach accessing various alkenyl heterocyclic compounds was developed using dimethyl malonate and 1,6-enynes in the presence of visible-light photoredox catalysis. The use of Ir(dtbbpy)(ppy)2PF6 as a photosensitizer enables carbon atom radical formation and initiates the cascade cyclization reaction under mild conditions.

11.
J Org Chem ; 87(6): 4455-4459, 2022 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-35258964

RESUMEN

A copper-catalyzed bromo-cyanomethylative cyclization of 1,6-enynes is demonstrated. The treatment of 2-bromoacetonitrile with CuI enables the alkyl radical generation and triggers the radical addition/cyclization/bromination sequence, giving various vinyl C-Br bonds containing functionalized heterocycles in good yields.

12.
J Org Chem ; 87(24): 16867-16872, 2022 Dec 16.
Artículo en Inglés | MEDLINE | ID: mdl-36475706

RESUMEN

Described herein is a copper-catalyzed efficient oxidative dearomatized functionalization of indoles by using alcohols as the nucleophiles. Various 3-alkoxy-2-oxindoles were accessible with good isolated yields. The synthetic potential applications are demonstrated by the large-scale reaction, as well as the derivatization of the desired 3-alkoxy substituted-2-oxindole products.

13.
Ann Noninvasive Electrocardiol ; 27(4): e12939, 2022 07.
Artículo en Inglés | MEDLINE | ID: mdl-35146844

RESUMEN

Hypoparathyroidism predisposes patients to hypocalcemia. Patients with hypoparathyroidism are thus at risk of electrocardiographic abnormalities, including T-wave alternans. T-wave alternans is poorly understood and lacks uniform diagnostic criteria. Its presence suggests myocardial electrical instability, and it has become an important sign for identifying patients at high risk of malignant arrhythmias and sudden cardiac death. We report a rare case of T-wave alternans with torsade de pointes due to hypocalcemia. The etiology of T-wave alternans may easily be overlooked. It should thus be thoroughly investigated to avoid misdiagnosis and poor outcomes.


Asunto(s)
Hipocalcemia , Hipoparatiroidismo , Torsades de Pointes , Arritmias Cardíacas/complicaciones , Electrocardiografía/efectos adversos , Humanos , Hipocalcemia/complicaciones , Hipocalcemia/diagnóstico , Hipoparatiroidismo/complicaciones , Hipoparatiroidismo/diagnóstico , Torsades de Pointes/complicaciones , Torsades de Pointes/diagnóstico
14.
Zhongguo Zhong Yao Za Zhi ; 47(6): 1618-1624, 2022 Mar.
Artículo en Zh | MEDLINE | ID: mdl-35347961

RESUMEN

Aconiti Kusnezoffii Radix Cocta is one of the most commonly used medicinal materials in Mongolian medicine. Due to the strong toxicity of Aconiti Kusnezoffii Radix Cocta, Mongolian medicine often uses Chebulae Fructus, Glycyrrhizae Radix et Rhizoma to reduce the toxicity, so as to ensure the curative effect of Aconiti Kusnezoffii Radix Cocta while ensuring its clinical curative effect, but the mechanism is not clear. The aim of this study was to investigate the effects of Chebulae Fructus, Glycyrrhizae Radix et Rhizoma and Aconiti Kusnezoffii Radix Cocta on the mRNA transcription and protein translation of cytochrome P450(CYP450) in the liver of normal rats. Male SD rats were randomly divided into negative control(NC) group, phenobarbital(PB) group(0.08 g·kg~(-1)·d~(-1)), Chebulae Fructus group(0.254 2 g·kg~(-1)·d~(-1)), Glycyrrhizae Radix et Rhizoma group(0.254 2 g·kg~(-1)·d~(-1)), Aconiti Kusnezoffii Radix Cocta group(0.254 2 g·kg~(-1)·d~(-1))and compatibility group(0.254 2 g·kg~(-1)·d~(-1),taking Aconiti Kusnezoffii Radix Cocta as the standard). After continuous administration for 8 days, the activities of total bile acid(TBA), alkaline phosphatase(ALP), amino-transferase(ALT) and aspartate aminotransferase(AST)in serum were detected, the pathological changes of liver tissue were observed, and the mRNA and protein expression levels of CYP1 A2, CYP2 C11 and CYP3 A1 were observed. Compared with the NC group, the serum ALP, ALT and AST activities in the Aconiti Kusnezoffii Radix Cocta group were significantly increased, and the ALP, ALT and AST activities were decreased after compatibility. At the same time, compatibility could reduce the liver injury caused by Aconiti Kusnezoffii Radix Cocta. The results showed that Aconiti Kusnezoffii Radix Cocta could inhibit the expression of CYP1 A2, CYP2 C11 and CYP3 A1, and could up-regulate the expression of CYP1 A2, CYP2 C11 and CYP3 A1 when combined with Chebulae Fructus and Glycyrrhizae Radix et Rhizoma. The level of translation was consistent with that of transcription. The compatibility of Chebulae Fructus and Glycyrrhizae Radix et Rhizoma with Aconiti Kusnezoffii Radix Cocta could up-regulate the expression of CYP450 enzyme, reduce the accumulation time of aconitine in vivo, and play a role in reducing toxicity, and this effect may start from gene transcription.


Asunto(s)
Sistema Enzimático del Citocromo P-450 , Hígado , Animales , Sistema Enzimático del Citocromo P-450/genética , Medicamentos Herbarios Chinos , Glycyrrhiza , Masculino , Extractos Vegetales , Ratas , Ratas Sprague-Dawley , Terminalia
15.
Angew Chem Int Ed Engl ; 61(52): e202208831, 2022 12 23.
Artículo en Inglés | MEDLINE | ID: mdl-36202761

RESUMEN

A direct strategy for the difunctionalization of alkenes, with acylation occurring at the more substituted alkene position, would be attractive for complex ketone synthesis. We report herein a reaction driven by a single photocatalyst that enables α-acylation in this way with the introduction of a fluoromethyl, alkyl, sulfonyl or thioether group at the ß-position of the alkene with high chemo- and regioselectivity under extremely mild conditions. Crucial to the success of this method are rate differences in the kinetics of radical generation through single-electron transfer (SET) between different radical precursors and the excited photocatalyst (PC*). Thus, the ß-position of the alkene is first occupied by the group derived from the radical precursor that can be generated most readily, and α-keto acids could be used as an electrophilic reagent for the α-acylation of alkenes.


Asunto(s)
Alquenos , Catálisis , Acilación , Indicadores y Reactivos
16.
Opt Lett ; 46(19): 4900-4903, 2021 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-34598229

RESUMEN

We propose and experimentally demonstrate a high-efficiency single-pixel imaging (SPI) scheme by integrating time-correlated single-photon counting (TCSPC) with time-division multiplexing to acquire full-color images at an extremely low light level. This SPI scheme uses a digital micromirror device to modulate a sequence of laser pulses with preset delays to achieve three-color structured illumination, then employs a photomultiplier tube into the TCSPC module to achieve photon-counting detection. By exploiting the time-resolved capabilities of TCSPC, we demodulate the spectrum-image-encoded signals, and then reconstruct high-quality full-color images in a single round of measurement. Based on this scheme, strategies such as single-step measurement, high-speed projection, and undersampling can further improve imaging efficiency.

17.
Allergy ; 76(2): 483-496, 2021 02.
Artículo en Inglés | MEDLINE | ID: mdl-32716553

RESUMEN

BACKGROUND: The impacts of chronic airway diseases on coronavirus disease 2019 (COVID-19) are far from understood. OBJECTIVE: To explore the influence of asthma and chronic obstructive pulmonary disease (COPD) comorbidity on disease expression and outcomes, and the potential underlying mechanisms in COVID-19 patients. METHODS: A total of 961 hospitalized COVID-19 patients with a definite clinical outcome (death or discharge) were retrospectively enrolled. Demographic and clinical information were extracted from the medical records. Lung tissue sections from patients suffering from lung cancer were used for immunohistochemistry study of angiotensin-converting enzyme II (ACE2) expression. BEAS-2B cell line was stimulated with various cytokines. RESULTS: In this cohort, 21 subjects (2.2%) had COPD and 22 (2.3%) had asthma. After adjusting for confounding factors, COPD patients had higher risk of developing severe illness (OR: 23.433; 95% CI 1.525-360.135; P < .01) and acute respiratory distress syndrome (OR: 19.762; 95% CI 1.461-267.369; P = .025) than asthmatics. COPD patients, particularly those with severe COVID-19, had lower counts of CD4+ T and CD8+ T cells and B cells and higher levels of TNF-α, IL-2 receptor, IL-10, IL-8, and IL-6 than asthmatics. COPD patients had increased, whereas asthmatics had decreased ACE2 protein expression in lower airways, compared with that in control subjects without asthma and COPD. IL-4 and IL-13 downregulated, but TNF-α, IL-12, and IL-17A upregulated ACE2 expression in BEAS-2B cells. CONCLUSION: Patients with asthma and COPD likely have different risk of severe COVID-19, which may be associated with different ACE2 expression.


Asunto(s)
Asma/epidemiología , COVID-19/complicaciones , Enfermedad Pulmonar Obstructiva Crónica/epidemiología , Anciano , Enzima Convertidora de Angiotensina 2/biosíntesis , Asma/inmunología , Asma/metabolismo , COVID-19/inmunología , Comorbilidad , Femenino , Humanos , Masculino , Persona de Mediana Edad , Prevalencia , Enfermedad Pulmonar Obstructiva Crónica/inmunología , Enfermedad Pulmonar Obstructiva Crónica/metabolismo , SARS-CoV-2
18.
Allergy ; 76(2): 551-561, 2021 02.
Artículo en Inglés | MEDLINE | ID: mdl-33040337

RESUMEN

BACKGROUND: The missing asymptomatic COVID-19 infections have been overlooked because of the imperfect sensitivity of the nucleic acid testing (NAT). Globally understanding the humoral immunity in asymptomatic carriers will provide scientific knowledge for developing serological tests, improving early identification, and implementing more rational control strategies against the pandemic. MEASURE: Utilizing both NAT and commercial kits for serum IgM and IgG antibodies, we extensively screened 11 766 epidemiologically suspected individuals on enrollment and 63 asymptomatic individuals were detected and recruited. Sixty-three healthy individuals and 51 mild patients without any preexisting conditions were set as controls. Serum IgM and IgG profiles were further probed using a SARS-CoV-2 proteome microarray, and neutralizing antibody was detected by a pseudotyped virus neutralization assay system. The dynamics of antibodies were analyzed with exposure time or symptoms onset. RESULTS: A combination test of NAT and serological testing for IgM antibody discovered 55.5% of the total of 63 asymptomatic infections, which significantly raises the detection sensitivity when compared with the NAT alone (19%). Serum proteome microarray analysis demonstrated that asymptomatics mainly produced IgM and IgG antibodies against S1 and N proteins out of 20 proteins of SARS-CoV-2. Different from strong and persistent N-specific antibodies, S1-specific IgM responses, which evolved in asymptomatic individuals as early as the seventh day after exposure, peaked on days from 17 days to 25 days, and then disappeared in two months, might be used as an early diagnostic biomarker. 11.8% (6/51) mild patients and 38.1% (24/63) asymptomatic individuals did not produce neutralizing antibody. In particular, neutralizing antibody in asymptomatics gradually vanished in two months. CONCLUSION: Our findings might have important implications for the definition of asymptomatic COVID-19 infections, diagnosis, serological survey, public health, and immunization strategies.


Asunto(s)
Anticuerpos Neutralizantes/inmunología , Anticuerpos Antivirales/inmunología , COVID-19/inmunología , Portador Sano/inmunología , SARS-CoV-2/inmunología , Adulto , Anciano , Anticuerpos Neutralizantes/sangre , Anticuerpos Antivirales/sangre , COVID-19/sangre , COVID-19/diagnóstico , Prueba de COVID-19/métodos , Portador Sano/sangre , Portador Sano/diagnóstico , Femenino , Humanos , Inmunoglobulina G/sangre , Inmunoglobulina G/inmunología , Inmunoglobulina M/sangre , Inmunoglobulina M/inmunología , Masculino , Persona de Mediana Edad
19.
J Org Chem ; 86(1): 1273-1280, 2021 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-33283502

RESUMEN

We herein described a selenylative cyclization reaction of enynes by the utilization of diselenides as radical sources. The visible-light irradiation of the reaction mixture enables the generation of the selenium atom radical to trigger the radical addition/cyclization/selenation sequences. Both terminal alkyne and internal alkyne derived 1,6-enynes were tested and suitable for the current synthetic protocol, delivering various kinds of selenium-containing cycles in good yields.

20.
Angew Chem Int Ed Engl ; 60(51): 26822-26828, 2021 12 13.
Artículo en Inglés | MEDLINE | ID: mdl-34586701

RESUMEN

1,4-Dicarbonyl compounds are intriguing motifs and versatile precursors in numerous pharmaceutical molecules and bioactive natural compounds. Direct incorporation of two carbonyl groups into a double bond at both ends is straightforward, but also challenging. Represented herein is the first example of 1,2-dicarbonylation of alkenes by photocatalysis. Key to success is that N(n-Bu)4+ not only associates with the alkyl anion to avoid protonation, but also activates the α-keto acid to undergo electrophilic addition. The α-keto acid is employed both for acyl generation and electrophilic addition. By tuning the reductive and electrophilic ability of the acyl precursor, unsymmetric 1,4-dicarbonylation is achieved for the first time. This metal-free, redox-neutral and regioselective 1,2-dicarbonylation of alkenes is executed by a photocatalyst for versatile substrates under extremely mild conditions and shows great potential in biomolecular and drug molecular derivatization.

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