Practical and Highly Selective C?H Functionalization of Structurally Diverse Ethers

A trityl ion mediated C H functionalization of ethers with a wide range of nucleophiles at ambient temperature has been developed. The reaction displays high chemoselectivity and good functional group tolerance. The protocol also exhibits excellent regio‐ and diastereoselectivities for the unsymmetric ethers, thus stereoselectively generating highly functionalized disubstituted 2,5‐trans tetrahydrofurans (THF), 2,6‐trans tetrahydropyrans (THP), 2,6‐trans dihydropyrans (DHP), and 1,3‐trans isochromans, and highlighting the capacity of the protocol in complex molecule synthesis.     

Palladium‐Catalyzed C(sp3)?H Activation: A Facile Method for the Synthesis of 3,4‐Dihydroquinolinone Derivatives

3,4‐Dihydroquinolinones were synthesized by the palladium‐catalyzed, oxidative‐addition‐initiated activation and arylation of inert C(sp³) H bonds. Pd(OAc)₂ and P(o‐tol)₃ were used as the catalyst and ligand, respectively, to improve the efficiency of the reaction. A further advantage of this reaction is that it could be performed in air. A relatively rare seven‐membered palladacycle was proposed as a key intermediate of the catalytic cycle.     

Palladium‐Catalyzed C?S Activation/Aryne Insertion/Coupling Sequence: Synthesis of Functionalized 2‐Quinolinones

The insertion of an aryne into a C S bond can suppress the addition of an S nucleophile to the aryne in the presence of palladium. Catalyzed by Pd(OAc)₂, a wide range of α‐carbamoyl ketene dithioacetals readily react with arynes to selectively afford functionalized 2‐quinolinones in high yields under neutral reaction conditions by a C S activation/aryne insertion/intramolecular coupling sequence. The attractive feature of the new strategy also lies in the versatile transformations of the alkythio‐substituted quinolinone products.     

Determination of glutathione in single HepG2 cells by capillary electrophoresis with reduced graphene oxide modified microelectrode

Determination of intracellular bioactive species will afford beneficial information related to cell metabolism, signal transduction, cell function, and disease treatment. In this study, the electrochemically reduced graphene oxide modified carbon fiber microdisk electrode (ER‐GOME) was used as a detector of CZE‐electrochemical detection and developed to detect glutathione (GSH). The electrocatalytic activity of the modified microelectrode was characterized by cyclic voltammetry. Under optimized experimental conditions, the concentration linear range of GSH was from 1 to 60 μM. When the S/N ratio was 3, the concentration detection limit was 1 μM. Compared with the unmodified carbon fiber microdisk electrode, the sensitivity was enhanced more than five times. With the use of this method, the average contents of GSH in single HepG2 cells were found to be 7.13 ± 1.11 fmol (n = 10). Compared with gold/mercury amalgam microelectrode, which was usually used in determining GSH, the electrochemically reduced graphene oxide modified carbon fiber microdisk electrode was friendly to environment for free mercury. Furthermore, there were several merits of the novel electrochemical detector coupled with CE, such as comparative repeatability, easy fabrication, and high sensitivity, hold great potential for the single‐cell assay.     

Efficient synthesis of functionalized 6-substituted-thiosalicylates via microwave-promoted Suzuki cross-coupling reaction

Functionalized 6-substituted-thiosalicylates are key intermediates for the synthesis of pyrimidinyl(thio)salicylic acids, a group of important herbicides targeting plant acetohydroxyacid synthase. Therefore, it is of great interest to develop an efficient method for the syntheses of 6-substituted-thiosalicylates. Herein, we have developed a direct and efficient method for the synthesis of functionalized 6-substituted-thiosalicylates (4) from aryl iodide (1) by using an improved microwave-assisted Suzuki cross-coupling reaction. Almost all the reactions proceeded smoothly and afforded moderate to excellent yields of products. Moreover, this protocol is obviously superior to the traditional available methods and could be utilized to synthesize pyrimidinyl(thio)salicylic acid and its derivatives.     

Synthesis of 1,4-diarylsubstituted 1,3-diynes through ligand-free copper-catalyzed oxidative decarboxylative homocoupling of aryl propiolic acids

An efficient method of ligand-free Cu-catalyzed oxidative decarboxylative homocoupling of aryl propiolic acids was developed. When CuI was employed as the catalyst and I₂ as the oxidant, the decarboxylative homocoupling reaction for C_sp–C_sp bond formation in DMSO underwent smoothly to afford the corresponding 1,4-disubstituted 1,3-dialkynes in good to excellent yields without any organic ligands. This catalytic system was applicable to aryl propiolic acids bearing different steric, electronic, and functional groups.     

One-pot reaction for the concise synthesis of spiro[benzofuran-2,2′-naphthalen]-1′-one derivatives

A novel one-pot two-step protocol has been developed to synthesize various spiro[benzofuran-2,2′-naphthalen]-1′-one derivatives from the three-component reaction of tetralones, 2-hydroxyphenyl functionalized α,β-unsaturated ketones, and iodine. One C–C bond and one C–O bond have formed during this process. The notable features of this protocol are simple and mild reaction conditions, applicable to a wide range of readily available starting materials, good yields (up to 91%), and excellent stereoselectivities (up to 97:3).     

Revisit of a series of ICT fluorophores: skeletal characterization,structural modification,and spectroscopic behavior

We have revisited the synthesis of a series of ICT fluorophores, which were reported to have a core structure of 8-oxo-8H-acenaphtho[1,2-b]pyrrol-9-carbonitrile. However, based on the 2D NMR and X-ray diffraction analysis, their core structure was corrected as 1-oxo-1H-phenalene-2,3-dicarbonitrile (1). Compound 1 shows a highly electron-deficient nature and can easily undergo oxidative S_NAr^H reaction on the naphthyl ring to produce a series of novel ICT fluorophores. The regioselectivity of this substitution reaction was studied by introduction of representative nucleophiles. Moreover, due to the strong rigidity and efficient ICT nature, the obtained fluorescent dyes display very good spectroscopic properties even in an aqueous environment.