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Palladium‐catalyzed thioesterification of (aza)indole‐tethered aryl iodides, Mo(CO)6, and sulfonyl chlorides is reported. A series of C2 thioester‐group substituted indoline‐fused ring compounds are constructed by an intramolecular Heck cyclization and carbonylation chemistry involving N‐(2‐iodobenzoyl)indole. The salient features of this three‐component cascade sequence include the use of solid Mo(CO)6 as the carbon monoxide source and good functional group tolerance. [ABSTRACT FROM AUTHOR]

A procedure utilizing [TBA][P(SiCl3)2] as P source for the synthesis of phosphinecarboxamides is presented. The synthesis involves the reaction of [TBA][P(SiCl3)2] with isocyanates. These compounds act as highly effective reagents for the subsequent phosphination of isocyanates, leading to the formation of phosphine(triscarboxamides). This reaction proceeds swiftly under mild and straightforward conditions, making it suitable for a wide range of commercially available isocyanates. [ABSTRACT FROM AUTHOR]

As a gasotransmitter, carbon monoxide can induce tumor cell apoptosis by reversing the Warburg effect. Carbon monoxide-releasing molecules (CORMs) are a promising option for CO administration, but how to deliver the threshold concentration of CO into the tumor tissue remains a challenge. A series of novel targeted CORMs combining glycyrrhetinic acid (GA) derivative conjugates with a lipophilic mitochondriotropic triphenylphosphonium cation (TPP+) moiety were synthesized and evaluated for their antitumor activities. Among the complexes, complex 2 possessed excellent antitumor activities in HepG2 cells with IC50 values of 12.18 ± 4.66 μM compared with 5-FU. It caused the production of reactive oxygen species and reduced the mitochondrial membrane potential against HepG2 cells. Western blot analysis showed that complex 2 up-regulated the expression of the Bax protein and down-regulated the expression of Bcl-2, activated caspase-3, and HO-1. The docking study demonstrated that complex 2 can interact with the Bcl-2 protein through hydrophobic interaction and hydrogen bonds. The aforementioned results indicated that complex 2 triggered cell apoptosis through a mitochondrial pathway. These results suggest that the complexes may be promising anticancer agent candidates. [ABSTRACT FROM AUTHOR]

A novel and facile method for the formation of C–S bonds via Mn(III) promoted cross-coupling reaction of disulfides with dialkyl phosphites under mild reaction conditions has been achieved. This strategy allows various dialkyl phosphites and disulfides to be transferred into the desired products in good to excellent yields. [ABSTRACT FROM AUTHOR]

C2‐functionalized pyrimidine derivative is a family of important nitrogen heterocyclic compounds due to their unique structure and multiple reaction sites. In this work, a novel method for the synthesis of C2‐functionalized pyrimidine derivatives through phenylalkynes and pyrimidine disulfides under ambient conditions is proposed. The reaction can be triggered by adding catalytic amounts of cesium fluoride, which is characterized by free‐catalyst and special activator. Importantly, this reaction has good compatibility with substrates substituted by electron‐donating and electron‐withdrawing groups at C4. Density functional theory (DFT) calculations also indicates that the production of C2‐functionalized pyrimidine derivatives is more favourable. [ABSTRACT FROM AUTHOR]

SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 7.73-7.67 (m, 1 H), 7.60-7.58 (m, 2 H), 7.51-7.49 (m, 1 H), 7.34-7.29 (m, 2 H), 7.16 (d, I J i = 7.9 Hz, 2 H), 2.34 (s, 3 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 8.46 (d, I J i = 5.2 Hz, 1 H), 7.68-7.66 (m, 1 H), 7.63-7.58 (m, 1 H), 7.43-7.41 (m, 2 H), 7.14-7.06 (m, 3 H), 2.31 (s, 3 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 7.89 (d, I J i = 8.0 Hz, 1 H), 7.80 (d, I J i = 8.0 Hz, 1 H), 7.67-7.63 (m, 2 H), 7.46-7.42 (m, 1 H), 7.36-7.32 (m, 1 H), 7.06-7.02 (m, 2 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 7.43 (d, I J i = 8.0 Hz, 2 H), 7.13 (d, I J i = 8.0 Hz, 2 H), 3.83 (t, I J i = 5.6 Hz, 2 H), 2.88-2.85 (m, 2 H), 2.32 (s, 3 H), 1.92 (s, 1 H). [Extracted from the article]

A reliable method for preparing P(III)‐arylphosphinecarboxamide derivatives from N‐arylphosphinecarboxamides and aryne precursors has been developed. This reaction was carried out without transition‐metal catalysts, and a series of unsymmetrically structured phosphinecarboxamide derivatives were obtained under mild conditions. In addition, the reaction is carried out under air atomosphere, and the corresponding P(III)‐aryl phosphinecarboxamide compounds are also stable in air. [ABSTRACT FROM AUTHOR]

This report describes the oxidative coupling reaction of dithiopyrimidines with phenylhydrazine hydrochlorides to synthesize a series of arylthiopyrimidine derivatives. The reaction does not require transition metals as catalysts, and uses organic dye rose bengal as photocatalyst and air as oxidant. The reaction conditions are mild and meet the requirements of green chemistry. In addition, the method has a wide scope of substrates and good tolerance of functional groups. The control experiment showed that the reaction may be a free radical mechanism, and the molecular weight of the intermediate was captured by high‐resolution mass spectrometry. [ABSTRACT FROM AUTHOR]

N-doped porous carbon (NC) was synthesized from sugar cane bagasse, which is a sustainable and widely available biomass waste. The preferred NC sample had a well-developed porous structure, a graphene-like surface morphology and different N species. More importantly, the heterogeneous carbocatalyst exhibited superior catalytic performance in the aerobic dehydrogenation of various heterocyclic nitrogen compounds (49 examples, up to 96% yield), similar to that of C3N4 and GO. Characterization by TEM, BET and XPS accompanied by the EPR analysis revealed that the enhanced catalytic properties of NC came from its high activation ability for both O2 and heterocyclic nitrogen, attributed to the porous structure and pyridinic N (N-6) species, respectively. [ABSTRACT FROM AUTHOR]

An efficient palladium-catalyzed Hiyama reaction between various pyrimidin-2-yl tosylates with organosilanes has been developed. The use of CuCl with TBAF as additive is essential for promotion of the construction of the carbon–carbon bond. This procedure shows wide functional group tolerance for electrophilic pyrimidin-2-yl tosylates and has been extended to aromatic amino-substituted pyrimidin-2-yl tosylates, affording the desired C2-aryl and alkenyl pyrimidine derivatives in good to excellent yields. [ABSTRACT FROM AUTHOR]

This report describes the electrocatalytic regioselective acyloxylation and halogenation of aromatic C(sp2)‐H bond in an undivided cell without any toxic or expensive metals. This electrocatalytic acyoxylation of phenyl ether resulted in chemoselective C−H bond functionalization to give a series of aryl ether products with acyloxy, hydroxyl and halogen group. In addition, cyclic voltammograms showed that the electrode was the first step to oxidize aromatic rings, and a possible mechanism was proposed based on the experimental results. [ABSTRACT FROM AUTHOR]

A novel copper-nanoparticle-decorated sulfur-based polymer, Cu@S-co-BIM, was designed and constructed for the chronoamperometric analysis of glucose with high sensitivity and selectivity. S-co-BIM was synthesized via inverse vulcanization as a stable conductive substrate that displayed extraordinary electrical conductivity. Copper nanoparticles were electrodeposited as the catalyst. Combining abundant active sites and the high conductivity of S-co-BIM with the excellent electrocatalytic abilities of copper nanoparticles, the Cu@S-co-BIM sensor significantly increased the selectivity and sensitivity towards glucose determination. The amperometric current linearly increased with the glucose concentration in the range of 1 μM–3.3 mM, with a detection limit of 0.32 μM. The proposed sensor exhibited high selectivity to glucose oxidation in the presence of various interfering species, such as ascorbic acid (AA), uric acid (UA), sodium chloride, fructose, xylose, and maltose. The as-prepared sensor also exhibited excellent reproducibility and long-term stability. This new method was successfully applied for the detection of glucose in serum and in commercial gluconate oral liquid with satisfactory results. In addition, the proposed composite materials might provide a new strategy for expanding the applications of sulfur-rich polymers in the field of sensing. [ABSTRACT FROM AUTHOR]

Methods for the synthesis of 1,2,4-triazolidines are scarce. Herein, we report a visible-light-promoted decarboxylative addition cyclization of N-aryl glycines and azobenzenes to access such important compounds. Using commercially available methylene blue (MB) as an organic photocatalyst, the reaction proceeded smoothly in the absence of transition-metal catalysts at ambient temperature, affording the corresponding products, 1,2,4-triaryl 1,2,4-triazolidines, in good to excellent yields. This work demonstrates a new synthetic application of readily available azobenenes and provides a novel strategy for constructing 1,2,4-triazolidines. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: This paper describes the first case of a reductive coupling reaction with indene, a non‐heteroatom olefin used as a reducing agent. The scope of the substrate is wide. The homo‐coupling, cross‐coupling, and synthesis of 12 and 14‐membered rings were realized. The control experiment, indene‐product curve and density functional theory calculations showed that the η3‐palladium indene intermediate was formed by C—H activation in the presence of cesium carbonate. We speculate that the final product was obtained through a Pd (IV) intermediate or aryl ligand exchange. In addition, we excluded the formation of palladium anion (Pd(0)−) intermediates. [ABSTRACT FROM AUTHOR]

Herein, the sulfhydrylation and oxylation of olefins were completed under visible light irradiation with iodine as catalyst, which realized more economical and green chemical conversion because of the absence of metal complexes or organic dyes. A series of bifunctional modifications of olefins were achieved with good yields by using diol derivatives and water as nucleophiles. In addition, the control experiments show that the reaction is a free radical process. [ABSTRACT FROM AUTHOR]