Rhodium(III)-Catalyzed Conjugate Addition of ß-CF3-Enones with Quinoline N-Oxides.

The site-selective incorporation of a trifluoromethyl group into biologically active molecules and pharmaceuticals has emerged as a central topic in medicinal chemistry and drug discovery. Herein, we demonstrate the rhodium(III)-catalyzed conjugate addition of ß-trifluoromethylated enones with quinoline N-oxides, which result in the generation of ß-trifluoromethyl-ß'-quinolinated ketones. The reaction proceeds under mild conditions with complete functional group tolerance. The synthetic applicability was showcased by successful gram-scale experiments and valuable synthetic transformations of coupling products.

Catalyst-Controlled C-H Allylation and Annulation of 2-Aryl Quinazolinones with 2-Methylidene Cyclic Carbonate.

The site-selective modification of quinazolinone as a privileged bicyclic N-heterocycle is an attractive topic in medicinal chemistry and material science. We herein report the ruthenium(II)-catalyzed C-H allylation of 2-aryl quinazolinones with 2-methylidene cyclic carbonate. In addition, tandem C-H allylation and annulation are achieved under rhodium(III) catalysis, resulting in the formation of tetracyclic quinazolinones including a tertiary carbon center. Post-transformations of the synthesized products demonstrate the potential of the developed methodology. A series of mechanistic investigations were also performed.

Probing multimodal light emission from Tb3+/Yb3+-doped garnet nanophosphors for lighting applications.

Herein we report the solution-combustion-method-synthesized Tb3+- and Tb3+/Yb3+-doped Gd3Ga5O12 nanophosphors, which possess luminescent and magnetic properties. The phase formation/crystal structure, and morphology of the prepared nanophosphors are studied using X-ray diffraction (XRD)/Raman spectroscopy and a field emission scanning electron microscope (FE-SEM), respectively. Tb3+/Yb3+-doped phosphor samples exhibit green emission with an intense band around 544 nm through downshifting (DS) and upconversion (UC) processes because of the 5D4 → 7F5 transition of Tb3+. In addition to this visible emission, these samples also show a NIR emission band around 1024 nm via the quantum cutting (QC) process due to the 2F5/2 → 2F7/2 transition of Yb3+. Emission decay measurements of the 5D4 → 7F5 transition of Tb3+ are performed to obtain the rate of energy transfer from Tb3+ to nearby Yb3+. Furthermore, using this energy transfer, the quantum cutting efficiencies were estimated. For their practical application, a selected sample was used to fabricate a LED device by combining the sample with a UV-C LED (274 nm). The obtained results, such as the activation energy (∼0.20 eV) and the high CRI value (78), suggest that the prepared sample can be utilized as a green-light-emitting agent in phosphor-coated (pc) WLEDs.

Polymer-Induced Emission-Active Fluorine-Embedded Carbon Dots for the Preparation of Warm WLEDs with a High Color Rendering Index.

Exploration of many strategies has continuously contributed to producing aggregation-induced red-emissive carbon dots (CDs). In this work, we designed fluorine-embedded (F-embedded) CDs from 1,2,4-triaminobenzene, thiourea, and ammonium fluoride (NH4F) exhibiting polymer-induced emission (PIE). The PIE phenomenon of fluorescent CDs is obtained in poly(vinyl alcohol) (PVA), showing emissions at 611 and 617 nm in the dispersed and solid states, respectively. The CDs exhibited a red shift of 28 nm in the PVA solution because PVA hydroxyl groups formed a robust bridge-like H-bonding network between CDs. The fluorine embedded in CDs enhanced the H-bond affinity toward PVA. It showed that this H-bond restricted the coupling of CDs' surface states and inhibited the nonirradiation transfer. For the solid state, surface PVA chains eliminated the π-π interaction of the conjugated core and constructed a self-quenching resistance polymeric system around CDs. As a result, CDs showed an unexpected red shift of fluorescence emission in PVA. Furthermore, white light-emitting diodes (WLEDs) have a correlated color temperature (CCT) of 5232 K, and a high color rendering index of 95 has been fabricated by integrating the red- and green-emissive films over the UV LEDs. Interestingly, the as-synthesized CDs showed room temperature phosphorescence (RTP), which enabled us to employ the CDs in double-security protection. Simultaneously, CDs have been used in fingerprint detection.

Perovskite La1-xKxCoO3-δ (0 ≤ x ≤ 0.5): a novel bifunctional OER/ORR electrocatalyst and supercapacitive charge storage electrode in a neutral Na2SO4 electrolyte.

The as-prepared La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) showed superior pseudocapacitive charge storage capacity in a neutral 0.5 M Na2SO4 electrolyte and superior electrocatalytic activities for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in a 1 M KOH electrolyte. 30% K doped p-type La0.7K0.3CoO3-δ presents superior OER activity with an overpotential of ∼335 mV at 10 mA cm-2 current rate in a 1 M KOH electrolyte. Additionally, La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) presents an excellent charge-storage capacitance in a neutral 0.5 M Na2SO4 electrolyte resulting in a gravimetric capacitance of the La0.5K0.5CoO3-δ electrode equivalent to 378 F g-1, 282 F g-1, 221 F g-1, 163 F g-1, and 74 F g-1 at a current density of 1 A g-1, 2 A g-1, 3 A g-1, 5 A g-1, and 10 A g-1, respectively. After 2500 continuous cycles of charge/discharge, the La0.5K0.5CoO3-δ//AC cell exhibits higher stability, capacitive retention (94%) and coulombic efficiency (97%). The gravimetric charge storage capacity of ASCs (La0.5K0.5CoO3-δ//AC) in the full cell mode showed capacitance equivalent to 308 F g-1, 287 F g-1, 238 F g-1, 209 F g-1 and 162 F g-1 at current densities of 1 A g-1, 2 A g-1, 3 A g-1, 5 A g-1 and 10 A g-1 in a neutral 0.5 M Na2SO4 electrolyte respectively. Maximum specific power equivalent to ∼6884 W kg-1 was observed at a current density of 10 A g-1 when the specific energy reached ∼57 W h kg-1 for the full cell. The double exchange mechanism coupled with stoichiometric oxygen defects present in the perovskite lattice seems to be operative behind the enhanced electrocatalytic OER properties, and additionally, it improves the charge storage kinetics of the La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) electrode in a neutral Na2SO4 electrolyte for supercapacitor application. This work presents a rational strategy for introducing facile oxygen ion defects into perovskite structured La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) to develop multifunctional electrode materials for a supercapacitor and energy conversion (OER/ORR) electrode of metal-air batteries.

Site-Selective C8-Alkylation of Quinoline N-Oxides with Maleimides under Rh(III) Catalysis.

The site-selective modification of quinolines and their analogs has emerged as a pivotal topic in medicinal chemistry and drug discovery. Herein, we describe the rhodium(III)-catalyzed C8-alkylation of quinoline N-oxides with maleimides as alkylating agents, resulting in the formation of bioactive succinimide-containing quinoline derivatives. The reaction proceeds under mild conditions with complete functional group tolerance.

Transition-Metal-Free Alkylation and Acylation of Benzoxazinones with 1,4-Dihydropyridines.

The direct functionalization of N-heterocycles is a vital transformation for the development of pharmaceuticals, functional materials, and other chemical entities. Herein, the transition-metal-free alkylation and acylation of C(sp2)-H bonds in biologically relevant 2-benzoxazinones with 1,4-dihydropyridines as readily accessible radical surrogates is described. Excellent functional group compatibility and a broad substrate scope were attained. Gram-scale reaction and transformations of the synthesized adducts via Suzuki coupling with heteroaryl boronic acids demonstrated the synthetic potential of the developed protocol.

Synthesis of π-Extended Heterocycles via Rh(III)-Catalyzed Oxidative Annulation of 5-Aryl Pyrazinones with Alkynes.

The Rh(III)-catalyzed C-H functionalization and subsequent oxidative annulation between 5-aryl pyrazinones and internal alkynes are reported. This protocol provides facile access to a wide range of pyrazinone-linked naphthalenes via the C(sp2)-H alkenylation and subsequent annulation. This transformation is characterized by mild conditions, simplicity, and excellent functional group compatibility. Notably, it is a first report of the utilization of pyrazinones as directing groups in C-H functionalization.

C-H Methylation of Iminoamido Heterocycles with Sulfur Ylides*.

The direct methylation of N-heterocycles is an important transformation for the advancement of pharmaceuticals, agrochemicals, functional materials, and other chemical entities. Herein, the unprecedented C(sp2 )-H methylation of iminoamido heterocycles as nucleoside base analogues is described. Notably, trimethylsulfoxonium salt was employed as a methylating agent under aqueous conditions. A wide substrate scope and excellent level of functional-group tolerance were attained. Moreover, this method can be readily applied to the site-selective methylation of azauracil nucleosides. The feasibility of gram-scale reactions and various transformations of the products highlight the synthetic potential of the developed method. Combined deuterium-labeling experiments aided the elucidation of a plausible reaction mechanism.

Deoxygenative Amination of Azine-N-oxides with Acyl Azides via [3 + 2] Cycloaddition.

A transition-metal-free deoxygenative C-H amination reaction of azine-N-oxides with acyl azides is described. The initial formation of an isocyanate from the starting acyl azide via a Curtius rearrangement can trigger a [3 + 2] dipolar cycloaddition of polar N-oxide fragments to generate the aminated azine derivative. The applicability of this method is highlighted by the late-stage and sequential amination reactions of complex bioactive compounds, including quinidine and fasudil. Moreover, the direct transformation of aminated azines into various bioactive N-heterocycles illustrates the significance of this newly developed protocol.

Ru(II)-Catalyzed C-H Hydroxyalkylation and Mitsunobu Cyclization of N-Aryl Phthalazinones.

Ruthenium(II)-catalyzed C(sp2)-H functionalization of N-aryl phthalazinones with a range of aldehydes and activated ketone is described. Initial formation of hydroxyalkylated phthalazinones and subsequent Mitsunobu cyclization provided facile access to biologically relevant indazolophthalazinones. The utility of this method is highlighted by synthetic transformations into a series of potentially bioactive scaffolds.

Phthalazinone-Assisted C-H Amidation Using Dioxazolones Under Rh(III) Catalysis.

The preparation of phthalazinone derivatives is pivotal for their utilization as pharmaceutical agents and other entities. Herein, we report the phthalazinone-assisted carbon-nitrogen bond forming reaction using dioxazolones as robust amidation sources under Rh(III) catalysis. The broad functional group tolerance and complete site-selectivity are observed. Notably, a series of transformations of synthesized compounds into biologically relevant N-heterocycles demonstrates the applicability of the developed methodology.

Ru(ii)-Catalyzed C-H addition and oxidative cyclization of 2-aryl quinazolinones with activated aldehydes.

The ruthenium(ii)-catalyzed cross-coupling reaction between 2-aryl quinazolinones and activated aldehydes is described. This method enables the site-selective hydroxyalkylation under redox-neutral conditions. Moreover, this protocol provides a facile access to various tetracyclic isoindoloquinazolinones by using Cu(OAc)2 as an external oxidant via C-H addition and subsequent intramolecular cyclization. A wide substrate scope and a high level of chemoselectivity as well as broad functional group tolerance are observed.

Ruthenium(II)-Catalyzed Site-Selective Hydroxymethylation of Indolines with Paraformaldehyde.

The facile synthesis of hydroxymethylated indole derivatives is crucial for their further development as pharmaceutical compounds and other synthetic purposes. Herein, we describe the ruthenium(II)-catalyzed hydroxymethylation of indolines and other N-heterocycles using paraformaldehyde as an abundant C1 feedstock. A wide substrate scope range and high levels of site selectivity as well as functional group tolerance were observed.

Allylic Acetals as Acrolein Oxonium Precursors in Tandem C-H Allylation and [3+2] Dipolar Cycloaddition.

The ruthenium(II)-catalyzed C-H functionalization of (hetero)aryl azomethine imines with allylic acetals is described. The initial formation of allylidene(methyl)oxoniums from allylic acetals could trigger C(sp2 )-H allylation, and subsequent endo-type [3+2] dipolar cycloaddition of polar azomethine fragments to deliver valuable indenopyrazolopyrazolones. The utility of this method is showcased by the late-stage functionalization of bioactive molecules such as estrone and celecoxib. Combined experimental and computational investigations elucidate a plausible mechanism of this new tandem reaction. Notably, the reductive transformation of synthesized compounds into biologically relevant diazocine frameworks highlights the importance of the developed methodology.

Synthesis of (2 H)-Indazoles through Rh(III)-Catalyzed Annulation Reaction of Azobenzenes with Sulfoxonium Ylides.

The rhodium(III)-catalyzed C-H functionalization followed by intramolecular annulation reactions between azobenzenes and sulfoxonium ylides is described. This protocol leads to the efficient formation of 3-acyl (2 H)-indazoles with a range of substrate scope. A high level of chemoselectivity and functional group tolerance of this transformation were also observed.

Ru(II)-Catalyzed C-H Aminocarbonylation of N-(Hetero)aryl-7-azaindoles with Isocyanates.

The ruthenium(II)-catalyzed C-H aminocarbonylation of N-(hetero)aryl-7-azaindoles with isocyanates is described. The excellent site selectivity at the ortho-position within the N-(hetero)aryl ring was observed to provide ortho-amidated N-(hetero)aryl-7-azaindoles under the mild reaction conditions. The resulting 7-azaindole derivatives can be readily transformed into 7-azaindoles containing carboxylic acid and alkyl amine functional groups.

Synthesis and Anti-inflammatory Evaluation of 2-Aminobenzaldehydes via Ir(III)-Catalyzed C-H Amidation of Aldimines with Acyl Azides.

The aldimine-directed C-H amidation of various arenes with N-acyl azides as amidation surrogates under cationic iridium(III) catalysis is described. This transformation efficiently provides a range of 2-aminobenzaldehyde derivatives with excellent site selectivity and functional group compatibility. The resulting 2-aminobenzaldehyde framework provides facile access to a range of biologically interesting heterocycles. In addition, all synthetic compounds were screened for anti-inflammatory activity against interleukin-1ß (IL-1ß) and tumor necrosis factor alpha (TNF-α) with lipopolysaccharide (LPS)-induced RAW264.7 cells. Generally, a range of ortho-amidated benzaldehydes displayed promising inhibitory activity against IL-1ß and TNF-α compared to dexamethasone as a positive control. Notably, compounds (3ae and 4ac) were found to exhibit potent anti-inflammatory activity stronger than that of dexamethasone.

Rhodium-Catalyzed [3 + 2] Annulation of Cyclic N-Acyl Ketimines with Activated Olefins: Anticancer Activity of Spiroisoindolinones.

The rhodium(III)-catalyzed redox-neutral coupling reaction of N-acyl ketimines generated in situ from 3-hydroxyisoindolinones with various activated olefins is described. This approach leads to the synthesis of bioactive spiroisoindolinone derivatives in moderate to high yields. In the case of internal olefins such as maleimides, maleates, fumarates, and cinnamates, spiroindanes were obtained by the [3 + 2] annulations reaction. In sharp contrast, acrylates and quinones displayed the ß-H elimination followed by Prins-type cyclization furnishing spiroindenes. The synthetic compounds were evaluated for in vitro anticancer activity against androgen-sensitive human prostate adenocarcinoma cells (LNCaP), human prostate adenocarcinoma cells (DU145), human endometrial adenocarcinoma cells (Ishikawa), human breast cancer cell (MCF-7), and triple negative human breast cancer cells (MDA-MB-231). Notably, quinone-containing spiroindenes displayed potent anticancer activity about 2- to 3-fold stronger than that of anticancer agent doxorubicin.

Synthesis and anti-inflammatory evaluation of N-sulfonyl anthranilic acids via Ir(III)-catalyzed C-H amidation of benzoic acids.

The iridium(III)-catalyzed ortho-C-H amidation of benzoic acids with sulfonyl azides is described. These transformations allow the facile generation of N-sulfonyl anthranilic acids, which are known as crucial scaffolds found in biologically active molecules. In addition, all synthetic products were evaluated for in vitro anti-inflammatory activity against interleukin-1ß (IL-1ß) and cyclooxygenase-2 (COX-2) with lipopolysaccharide (LPS)-induced RAW264.7 cells. Notably, compounds 4c and 4d, generated from p-OMe- and p-Br-sulfonyl azides, were found to display potent anti-inflammatory property stronger than that of well-known NSAIDs ibuprofen.