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1.
J Org Chem ; 89(14): 10047-10053, 2024 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-38951997

RESUMEN

We have successfully synthesized a series of bidentate ligands by utilizing 2-(trimethylsilyl)phenyl trifluorosulfonate as a precursor for the benzyl group. This method proceeded by inserting a polythiourea into the C═S π-bond, intramolecular ring proton migration, and ring opening. Salient features of this strategy are mild reaction conditions, a novel product structure, excellent stereochemistry, and a good functional group tolerance. Furthermore, a series of density functional theory calculations were performed to gain insights into the transfer mechanism.

2.
J Org Chem ; 89(11): 7741-7746, 2024 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-38741558

RESUMEN

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade reaction undergoes a sequence of oxidative addition, unsaturated bond migration, carbonyl insertion, and nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines and aliphatic amines could proceed smoothly in this transformation under one atm of CO.

3.
Org Biomol Chem ; 2024 Aug 20.
Artículo en Inglés | MEDLINE | ID: mdl-39161268

RESUMEN

Aromatic 1,2,4-diazaphospholes featuring distinct hybrid-mode nitrogen atoms (N(λ3σ2), N(λ3σ3)) and low-valent phosphorus atoms (λ3σ2) exhibited the characteristic of serving as unique hybrid ligands. This study presented a one-pot reaction involving the base-promoted stepwise cyclization of hydrazonoyl chlorides and [Bu4N][P(SiCl3)2] to yield 1,2,4-diazaphospholes, providing an effective method for synthesizing such compounds.

4.
J Org Chem ; 88(3): 1403-1410, 2023 Feb 03.
Artículo en Inglés | MEDLINE | ID: mdl-36656018

RESUMEN

A nickel-catalyzed three-component tandem radical cyclization reaction of aryl bromides with 1,3-enynes and aryl boric acids to construct γ-lactam-substituted allene derivatives has been described. This protocol provides lactam alkyl radicals through the free radical cyclization process, which can be effectively used to participate in the subsequent multicomponent coupling reaction so that 1,3-enynes could directly convert into corresponding poly-substituted allene compounds. In addition, this efficient method enjoys a broad substrate scope and provides a series of 1,5-difunctionalized allenes in a one-pot reaction.

5.
J Org Chem ; 88(3): 1786-1795, 2023 Feb 03.
Artículo en Inglés | MEDLINE | ID: mdl-36657999

RESUMEN

Carbazole, as one of the most important organic frameworks, has been used in optoelectronic materials and biochemistry. However, the synthesis of C4-substituted carbazole has always been an unsolved problem. This report describes the one-step synthesis of C4-aminated carbazoles and their derivatives through the series reaction of C-H amination and arylation. The substrate scope is wide. C4-Amino carbazoles substituted by C2, C6, C7, and C8 methyl groups, especially carbazole derivatives of fused rings, pyridine, and dibenzofuran, can be synthesized.

6.
J Org Chem ; 88(23): 16539-16546, 2023 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-37947111

RESUMEN

This report describes the use of a simple Pd/NBE catalytic system to achieve ortho C-H oxylation and phosphonylation and other functionalizations of aryl iodide through templated conversion reactions. Dimethylamine is introduced in the ortho-site of aryl iodide through C-H amination, and aryl dimethylamine is quickly converted to methyl quaternary ammonium salt precipitation. Methyl quaternary ammonium salt avoids Hofmann elimination in subsequent functionalization. This method solves various ortho functionalization reactions of aryl iodide that have not been achieved for a long time in the field of Pd/NBE chemistry indirectly.

7.
Org Biomol Chem ; 21(12): 2499-2503, 2023 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-36880434

RESUMEN

Sulfur-containing organophosphorus molecules have played a pivotal role in organic synthesis, pharmaceutical pesticides and functional materials, thereby motivating researchers worldwide to establish S-P bonds from more environmentally friendly phosphorus sources. In this study, a novel method was developed for constructing S-P bonds, specifically by reacting the inorganic phosphorus derivative TBA[P(SiCl3)2] with sulfur-containing compounds under mild conditions. This method demonstrates the advantages of low energy consumption, mild reaction conditions and environmental friendliness. Moreover, this protocol-as a green synthesis method to replace the use of white phosphorus in the production of organophosphorus compounds (OPCs)-achieved the functional conversion of "inorganic phosphorus to organic phosphorus", in line with the national green development strategy.

8.
Org Biomol Chem ; 21(43): 8744-8748, 2023 Nov 08.
Artículo en Inglés | MEDLINE | ID: mdl-37873567

RESUMEN

A p-TsOH/halotrimethylsilane facilitated cycloketonization of γ-hydroxyl ynones is detailed. This methodology enables the one-step synthesis of polysubstituted 3(2H)-furanone products. It is remarkable that the reaction exhibits excellent regio- and chemoselectivity by the addition of very small quantities of p-toluenesulfonic acid and water.

9.
J Org Chem ; 87(21): 14536-14543, 2022 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-36269896

RESUMEN

We report a cathodic reduction-dominated electrochemical approach for the hydrogenation of azobenzenes in dichloromethane. With cheap and readily available N,N-diisopropylethylamine as a catalytic mediator, the reaction proceeded smoothly in a simple undivided cell under constant-current electrolysis. A series of azobenzenes were successfully reduced to the corresponding hydrazobenzenes in moderate to high yields at room temperature. Preliminarily mechanistic studies indicate that solvent dichloromethane acts as a hydrogen source. The use of a common solvent as a hydrogen source, no need for stoichiometric mediators or metallic reductants, and mild conditions make this work a more straightforward and sustainable protocol for hydrogenation of azobenzenes.

10.
Org Biomol Chem ; 20(25): 5139-5144, 2022 06 29.
Artículo en Inglés | MEDLINE | ID: mdl-35707997

RESUMEN

Visible-light-promoted cyclization and aromatization of chalcones with 2-mercaptobenzimidazoles have been successfully developed to obtain diverse imidazo[2,1-b]thiazoles, and C-S and C-N bonds were constructed in one step. The reaction uses oxygen in the air as an oxidant, and the method does not need an external photocatalyst or a transition metal catalyst. The strategy features mild conditions, a simple system, readily accessible feedstocks, and a friendly environment. UV absorption spectroscopy and control experiments have shown that the reaction mechanism involves the formation of an electron-donor-acceptor (EDA) complex from thiolate anions and chalcones. In order to verify the mechanism, we studied the structure and HOMO/LUMO of the EDA complex by density functional theory (DFT) calculations. The results show that the π-π stacking between chalcones and 2-mercaptobenzimidazoles will cause a red shift of the UV absorption wavelength in the presence of Cs2CO3, and also provide a theoretical basis for the electron transfer of EDA complexes.


Asunto(s)
Chalconas , Bencimidazoles , Chalconas/química , Ciclización , Luz , Oxidantes
11.
J Org Chem ; 86(6): 4804-4811, 2021 Mar 19.
Artículo en Inglés | MEDLINE | ID: mdl-33688729

RESUMEN

A visible-light-promoted transfer hydrogenation of azobenzenes has been developed. In the presence of B2pin2 and upon visible-light irradiation, the reactions proceeded smoothly in methanol at ambient temperature. The azobenzenes with diverse functional groups have been reduced to the corresponding hydrazobenzenes with a yield of up to 96%. Preliminary mechanistic studies indicated that the hydrogen atom comes from the solvent and the transformation is achieved through a radical pathway.

12.
Bioorg Chem ; 107: 104621, 2021 02.
Artículo en Inglés | MEDLINE | ID: mdl-33465671

RESUMEN

In this study, two series of novel carbon monoxide-releasing molecules (CO-RMs) containing Co were designed and synthesized. The synthesized complexes were characterized by IR, ESI-MS, 1H NMR and 13C NMR spectroscopies. The antitumor activity of all complexes on HepG2 cells, Hela cells and MDA-MB-231 cells were assayed by MTT. IC50 values of complexes 1-13 were 4.7-548.6 µM. Among these complexes, complex 1 was presented with a high selectivity to HepG2 cells (IC50 = 4.7 ± 0.76 µM). Compared with iCORM (inactive CORM), CORM (complex 1) showed a remarkable activity against tumor cells owing to co-effect of CO and the ligand of COX-2 inhibitor. In addition, complex 1 increased ROS in mitochondria and caused a decrease of dose-dependent mitochondrial membrane potential against HepG2 cells. Complex 1 down-regulated the expression of COX-2 protein in western blot analysis. The molecular docking study suggested that the complex 1 formed a hydrogen bond with amino acid R120 in the active site of the Human cyclooxygenase-2 (COX-2). Therefore, the complex 1 could induce apoptosis of HepG2 cells through targeting COX-2 and mitochondria pathways, and it maybe a potential therapeutic agent for cancer.


Asunto(s)
Antineoplásicos/síntesis química , Monóxido de Carbono/metabolismo , Complejos de Coordinación/química , Antineoplásicos/metabolismo , Antineoplásicos/farmacología , Apoptosis/efectos de los fármacos , Sitios de Unión , Puntos de Control del Ciclo Celular/efectos de los fármacos , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/metabolismo , Complejos de Coordinación/farmacología , Ciclooxigenasa 2/química , Ciclooxigenasa 2/metabolismo , Inhibidores de la Ciclooxigenasa 2/química , Inhibidores de la Ciclooxigenasa 2/metabolismo , Inhibidores de la Ciclooxigenasa 2/farmacología , Diseño de Fármacos , Ensayos de Selección de Medicamentos Antitumorales , Humanos , Potencial de la Membrana Mitocondrial/efectos de los fármacos , Mitocondrias/efectos de los fármacos , Mitocondrias/metabolismo , Simulación del Acoplamiento Molecular , Estructura Terciaria de Proteína , Especies Reactivas de Oxígeno/metabolismo
13.
J Org Chem ; 84(7): 4165-4178, 2019 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-30835121

RESUMEN

A AgSCF3/Na2S2O8-promoted trifluoromethylthiolation/cascade cyclization of o-propargyl arylazides (or o-alkynyl benzylazides) triggered by a carbon-carbon triple bond is reported. This strategy provides the synthesis of valuable SCF3-substituted quinoline and isoquinoline systems via the construction of one C(sp2)-SCF3 bond and one C-N bond within one process.

14.
Org Biomol Chem ; 17(9): 2379-2383, 2019 02 27.
Artículo en Inglés | MEDLINE | ID: mdl-30724938

RESUMEN

K2CO3-catalyzed thio-Michael addition using quinoline-2-thiones and α,ß-unsaturated carbonyl compounds was used to assess the chemoselective construction of C-S and S-S bonds under mild reaction conditions in different solvents. The C-S bond showed a better chemoselective construction in EtOH whereas the S-S bond showed a better chemoselective construction in 1,4-dioxane. The corresponding products, generated from the reaction, presented a significant solvent-controlling effect.

15.
Org Biomol Chem ; 16(48): 9472-9476, 2018 12 12.
Artículo en Inglés | MEDLINE | ID: mdl-30516792

RESUMEN

Since esters are important organic synthesis intermediates, an environmentally friendly oxone catalyzed-esterification of carboxylic acids with alcohols has been developed. A series of carboxylic acid esters are obtained in high yield. This strategy requires mild reaction conditions, providing an attractive alternative for the construction of valuable carbonyl esters. Electron-rich and electron-deficient groups are compatible with the standard conditions and a variety of substrates are demonstrated. Moreover, the reaction could easily be adapted to typical prodrugs, drugs and gram-scale synthesis.

16.
Chem Rec ; 16(1): 435-44, 2016 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-26805726

RESUMEN

The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner.

17.
Org Biomol Chem ; 14(8): 2395-8, 2016 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-26821885

RESUMEN

The copper(i)-promoted cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with aromatic amines and aliphatic amines to deliver C-N coupling products in moderate to good yields is reported in this paper. Central to this strategy is the conversion of disulfides into aryl- and alkyl amines by a copper-promoted chemoselective C-S bond cleavage.

18.
Org Lett ; 26(9): 1985-1990, 2024 Mar 08.
Artículo en Inglés | MEDLINE | ID: mdl-38393365

RESUMEN

Herein, we disclosed a highly chemoselective synthesis of quinoline-2-one and quinoline-2-thione derivatives using EtOS2K as the C1 source. Quinoline-2-one derivatives were synthesized selectively with NaCl as a catalyst in the solvent DMSO/H2O, while quinoline-2-thione derivatives were produced without the need for any catalyst in an environmentally friendly solvent EtOH/H2O. The reaction conditions were mild and had good functional group tolerance.

19.
Org Lett ; 26(17): 3575-3580, 2024 May 03.
Artículo en Inglés | MEDLINE | ID: mdl-38636450

RESUMEN

We introduce switchable chemoselectivity strategies based on the hydrazone phosphaketene intermediate to synthesize three classes of 1,2,4-diazaphosphol derivatives. First, the five-membered heterocyclic P and O anion intermediates acted as nucleophilic agents in the selective construction of C-P and C-O bonds. Second, the phosphinidene served as a phosphorus synthon, allowing for the formation of C-P and C-N bonds. Finally, a stepwise mechanism, supported by DFT calculations, was invoked to explain the reaction selectivity.

20.
Org Lett ; 2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-39235769

RESUMEN

The Narasaka-Heck reaction is one of the most straightforward methods for constructing pyrroline derivatives. Herein, we report a novel nickel-catalyzed three-component carbonylation reaction, which cleverly realizes the continuous construction of C(sp3)-N bonds and C(sp3)-C(sp2) bonds and effectively promotes the synthesis of acyl-substituted pyrroline derivatives. Furthermore, this strategy not only expands the conversion pathway of γ,δ-unsaturated oxime esters but also provides a new method for the synthesis of nitrogen-containing heterocyclic compounds.

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