Synthesis of Benzo[c]cinnolinium Salts from 2-Azobiaryls by Copper(II) or Electrochemical Oxidation.

Synthesis of benzo[c]cinnolinium salts by copper(II)-promoted or electrochemical oxidation of 2-azobiaryls is described. A variety of diversely functionalized benzo[c]cinnolinium salts were easily constructed by this strategy with excellent functional group tolerance and high efficiency. An interesting fluorescence centered at 571 nm is revealed by a benzo[c]cinnolinium salt with electron push-pull substitutions. The mechanism is proposed to go through single-electron transfer driven by oxidant and intramolecular cyclization via nucleophilic addition, followed by an anion exchange.

Green and Regioselective Approach for the Synthesis of 3-Substituted Indole Based 1,2-Dihydropyridine and Azaxanthone Derivatives as a Potential Lead for SARS-CoV-2 and Delta Plus Mutant Virus: DFT and Docking Studies.

Great attempts have been done for the development of novel antiviral compounds against SAR-CoV-2 to end this pandemic situation and save human society. Herewith, we have synthesized 3-substituted indole/2-substituted pyrrole 1,2-dihydropyridine and azaxanthone scaffolds using simple, commercially available starting materials in a one-pot, green, and regioselective manner. Further, the regioselectivity of product formation was confirmed by various studies such as controlled experiments, density functional theory (DFT), Mulliken atomic charge, and electrostatic potential (ESP) surface. In addition, 3-substituted indole 1,2-dihydropyridine was successfully converted into a biologically enriched pharmacophore scaffold, viz., indolylimidazopyridinylbenzofuran scaffold, in excellent yield. Moreover, the synthesized 3-substituted indole 1,2-dihydropyridine/2-substituted pyrroles were analyzed in docking studies for anti-SARS-CoV-2 properties against their main protease (Mpro) and anti-Delta plus properties against their protein of the Delta plus K417N mutant. Further, the drug-likeness prediction was analyzed by the Lipinski rule and other pharmacokinetic properties like absorption, distribution, metabolism, excretion, and toxicity using preADMET prediction. Interestingly, the docking results show that out of 20 synthesized compounds, 5 of them for Mpro of SAR-CoV-2 and 9 of them for 7NX7 spike glycoprotein's A chain of Delta plus K417N show greater binding affinity when compared with remdesivir that is the first to receive FDA approval and is currently used as a potent drug for the treatment of COVID-19. These results suggest that indole/pyrrole substituted 1,2-dihydropyridine derivatives are capable of combating SARS-CoV-2 and its Delta plus mutant.

A Highly Conductive n-Type Coordination Complex with Thieno[3,2-b]thiophene Units: Facile Synthesis, Orientation, and Thermoelectric Properties.

An organometallic nickel complex containing thieno[3,2-b]thiophene units was designed and synthesized. Composite films of the resulting nickel complex and polyvinylidene difluoride, which can be fabricated via a simple solution process under atmospheric conditions, exhibit remarkably high n-type conductivity (>200 S cm-1). Moreover, the thermoelectric power factor of the n-type composite film was proven to be air stable. A grazing-incidence wide-angle X-ray diffraction analysis indicated a significant impact of introducing the thieno[3,2-b]thiophene core into the backbone of the nickel complex on the orientation within the composite films.

Crystal structure and fluorescence of 1-[8-phenyl-9-(phenyl-ethyn-yl)-4H-benzo[def]carbazol-4-yl]ethan-1-one.

The crystal of the title compound, C60H38N2O2, which crystallizes in the monoclinic space group P21/n, was obtained by thermal evaporation of a 1:1 di-chloro-methane and hexa-nes solution of the pure compound. The crystal structure is stabilized by π-π inter-actions between benzo[def]carbazole moieties and carbon-yl-carbonyl inter-actions between the two acetyl groups.

Promoting the Efficiency and Stability of Nonfullerene Organic Photovoltaics by Incorporating Open-Cage [60]Fullerenes in the Nonfullerene Nanocrystallites.

The device efficiency of PM6:Y6-based nonfullerene organic solar cells is fast advanced recently. To maintain organic solar cells (OSCs) with high power conversion efficiency over 16% in long-term operation, however, remains a challenge. Here, a novel non-volatile additive, an open-cage [60]fullerene (8OC60Me), is incorporated into PM6:Y6-based OSCs for high-performance with high durability. With optimized addition of 1.0 wt % 8OC60Me, the PCE value of PM6:Y6/8OC60Me OSCs can be promoted to 16.5% from 15.0%. Most strikingly, such a high PCE performance can maintain nearly 100% for over 500 h at room temperature; at an elevated operation temperature of 80 °C, the PCE can be stabilized above 15.0% after 45 h of operation. Grazing incidence small- and wide- angle X-ray scattering studies reveal improved orientation and crystallinity of Y6 in a fractal-like network structure of PM6 in PM6:Y6/8OC60Me films under in situ annealing, parallel to the enhanced electron mobility. Analysis of charge distributions lines up possible van der Waals interaction between the thienyl/carbonyl moiety of 8OC60Me and difluorophenyl-based FIC-end groups of Y6. This result is of great contrast to those devices with the best-selling PC61BM as the additives─8OC60Me might be of interest to be incorporated into future Y6-based OSCs for concomitantly improved PCE and excellent stability.

Phosphine-Mediated [4 + 3] Annulation of Diynoates and 2-Arylidene Indane-1,3-diones: Access of Indeno[1,2-b]oxepin-4-ylidenes and Beyond.

A novel unprecedented triphenylphosphine-mediated [4 + 3] annulation reaction of 2-benzylidene indane-1,3-diones and -diynoates through initial phosphine α-addition was discovered and found to result in biologically interesting indeno[1,2-b]oxepin-4-ylidenes in up to 75% yield. The seven-membered separable Z and E isomeric oxepins were confirmed using single-crystal X-ray diffraction.

p-Tetrafluorophenylene Divinylene-Bridged Nonfullerene Acceptors as Binary Components or Additives for High-Efficiency Organic Solar Cells.

In this study, we designed, synthesized, and characterized an A-D-A'-D-A-type indacenodithienothiophene (IDTT)-based molecular acceptor that exhibited a broader absorption range and higher lowest unoccupied molecular orbital energy level with a nearly comparable band gap compared to a well-known electron acceptor IT-M. The designed electron-deficient molecular acceptor FB-2IDTT-4Cl with a fluorinated benzene tether (FB), that is, p-tetrafluorophenylene divinylene, demonstrated long-wavelength absorption and high hole and electron charge mobility in the thin films blended with the electron donor PBDB-T for an inverted organic photovoltaic (OPV) binary device, resulting in a maximum power conversion efficiency (PCE) of 11.4%. Such a performance is comparably as high as that of the device with PBDB-T:IT-M, and particularly, it was 18.8% higher than that of the devices with ITIC-4Cl as the acceptor (PCE 9.1% ± 0.5%) and 24.9% higher than that of the devices with the thiophene-flanked benzothiadiazole-bridged acceptor CNDTBT-IDTT-FINCN (PCE 9.01% ± 0.13%). Furthermore, varying the illumination intensity from 200 to 2000 lux increased the Jsc and Voc values as well as the FF values, thus leading to increased PCE levels. In addition, the best PCE of the PM6:Y6 device with 1% FB-2IDTT-4Cl as additives was 16.9%. Our stability test showed that the PM6:Y6 standard device efficiency downgraded very soon either at room temperature or under thermal-annealing conditions. However, with the addition of 1% FB-2IDTT-4Cl as additives, the device efficiency still can be maintained at 90-95% in 500 h at room temperature and 95% at 20 h and 85-95% in 45 h at an annealing temperature of 80 °C. These findings demonstrate FB-2IDTT-4Cl to be a promising candidate as an electron acceptor with a fluorinated π-bridging fused-ring design for OPV applications.

TfOH-promoted Classical Nazarov-type Cyclization of Benzofulvenes: Synthesis of Polycyclic 5H,10'H-spiro[benzo[k]phenanthridine-5,6'-dibenzopentalenes].

The reaction of o-benzofulvene with TfOH leads to intramolecular cyclization through novel C-C and C-N bond formation, resulting in the formation of 5H,10'H-spiro[benzo[k]phenanthridine-5,6'-dibenzopentalene]. This protocol provides a new molecular framework with reasonable to excellent yields and tolerates various electron-withdrawing/donating substituents. This method yields diastereoselectivity of up to >20:1. Furthermore, it is free of bases, oxidants, and metals and proceeds under mild reaction conditions, which are favorable for synthetic organic chemistry.

Pd-Catalyzed Redox-Neutral C-N Coupling Reaction of Iminoquinones with Electron-Deficient Alkenes without External Oxidants: Access of Tertiary (E)-Enamines and Application to the Synthesis of Indoles and Quinolin-4-ones.

A novel and efficient reductive N-alkenylation of iminoquinones with electron-deficient olefins has been successfully developed by Pd(II)-catalyzed redox-neutral reactions, which provides a synthesis of tertiary (E)-enamines. We further demonstrate that the tertiary enamines can be converted to multifarious N-heterocyclic compounds, indoles, and quinolones in good yields.

Cascade One-Pot Synthesis of Orange-Red-Fluorescent Polycyclic Cinnolino[2,3-f]phenanthridin-9-ium Salts by Palladium(II)-Catalyzed C-H Bond Activation of 2-Azobiaryl Compounds and Alkenes.

Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C-H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2-azobiaryls with alkenes to give orange-red-fluorescent cinnolino[2,3-f]phenanthridin-9-ium salts and 15H-cinnolino[2,3-f]phenanthridin-9-ium-10-ide is proposed to involve ortho C-H olefination of the 2-azobiaryl compound with the alkene, intramolecular aza-Michael addition, concerted metalation-deprotonation (CMD), reductive elimination, and oxidation.

Synthesis, Isolation, and Characterization of Mono- and Bis-norbornene-Annulated Biarylamines through Pseudo-Catellani Intermediates.

A palladium-catalyzed C-H functionalization of an external ring of N-acyl 2-aminobiaryl with bicyclo[2.2.1]hept-2-ene (norbornene) via multiple C-H bond activations was developed. This study is the first report of the formation of bis-norbornene annulated biarylamines isomers ( syn-3a'/ anti-3a' = 36:64) from multiple C-H bond functionalizations. Additionally, nondirected C-H bond functionalization at the C-4' position with alkenes rendered complete C-H functionalization of five C-H bonds that formed a stable hexasubstituted benzene ring.

Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4 + 2] Annulation.

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (MI/MIII, M = Co and Rh) generally favor a [3 + 2] cyclization pathway, whereas those involving higher oxidation states (MIII/MV) proceed through a [4 + 2] cyclization pathway. A catalytic cycle with novel MIII/MV as a crucial species was successfully revealed for isoquinolinium salts synthesis, in which highly valent MV was encountered not only in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

Palladium(II)-Catalyzed Mono- and Bis-alkenylation of N-Acetyl-2-aminobiaryls through Regioselective C-H Bond Activation.

We developed palladium-catalyzed oxidative coupling of olefins with N-acyl 2-aminobiaryls through a sequence of ortho C-H bond activation/alkene insertion/reductive elimination. Furthermore, we controlled the selectivity of mono- and bis-alkenylation products with the solvent effect. The developed protocol was promising for a broad substrate scope ranging from activated olefins with a wide variety of functional groups to unactivated olefins.

Low-temperature, simple and efficient preparation of perovskite solar cells using Lewis bases urea and thiourea as additives: stimulating large grain growth and providing a PCE up to 18.8.

We demonstrated that two Lewis bases - urea and thiourea - acted as efficient additives for CH3NH3(MA)PbI3-x Cl x and MAPbI3 perovskite solar cells (PSCs) and observed a significant increase in PCE for the MAPbI3 devices in the presence of 1% urea with a remarkable PCE of 18.8% using an extremely low annealing temperature (85 °C).

Palladium-Catalyzed C-H Bond Activation by Using Iminoquinone as a Directing Group and an Internal Oxidant or a Co-oxidant: Production of Dihydrophenanthridines, Phenanthridines, and Carbazoles.

A palladium-catalyzed C-H bond activation reaction, via a redox-neutral pathway, for the preparation of dihydrophenanthridine, phenanthridine, and carbazole derivatives from biaryl 2-iminoquinones is developed. The preinstalled iminoquinone was designed to act as a directing group for ortho C-H activation and an internal oxidant or a co-oxidant. This catalysis proceeded through the following sequence: C-H bond activation, coordination and insertion of activated olefins, ß-hydride elimination, H-shift, insertion, and protonation or ß-hydride elimination. In addition, carbazoles can be prepared efficiently by using this method without the addition of external oxidants.

Iptycenes with an acridinone motif developed through [4+2] cycloaddition of tethered naphthalene and iminoquinone via a radical reaction.

A new class of iptycenes was developed by combining 2-(naphthalen-1-yl)anilines and p-benzoquinones through copper(ii)-mediated radical cyclisation. This unusual cyclisation reaction resulted in the robust and efficient syntheses of iptycenes with an acridinone motif. These iptycenes can be further transformed into planar acridinone heterocyclics through the Diels-Alder reaction.

Tricyclohexylphosphine-Catalyzed Cycloaddition of Enynoates with [60]Fullerene and the Application of Cyclopentenofullerenes as n-Type Materials in Organic Photovoltaics.

The tricyclohexylphosphine-catalyzed [3 + 2] cycloaddition of (E)-alkyl 5-substituted phenylpent-4-en-2-ynoates with [60]fullerene was studied. This reaction undergoes an initial 1,3-addition of phosphines toward the α-carbons of enynoates. Subsequent cycloaddition of the generated 1,3-dipoles with [60]fullerene and elimination of tricyclohexylphosphines resulted in cyclopentenofullerenes in 20-43% yields. The isolated cyclopentenofullerenes were observed to serve as n-type materials in organic photovoltaics, providing a maximum average power conversion efficiency of 3.79 ± 0.29% upon embedding with P3HT in the active layer.

Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles generated highly substituted cyclopentenes through an unexpected phosphine α-addition-δ-evolvement of an anion pathway.

Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles provide highly substituted syn-selective cyclopentenes appending the phosphorus ylide moiety in good yield with a diastereoselectivity of up to 100% through resonance-derived 1,5-dipolar species as the key intermediates, via the nucleophilic α(δ')-attack of phosphines toward enynedioates followed by addition to benzylidene malononitriles and 5-exo-dig cyclization. Through computational analyses, the overall reactions for the formation of syn- and anti-diastereomers are both exothermic with 65.6 and 66.3 kcal mol(-1) at the B3LYP-D3/6-31G(d) level of theory and were found to be kinetically controlled, which favours the formation of syn-diastereomers.

Multicomponent reactions of phosphines, diynedioates, and aryl aldehydes generated furans appending reactive phosphorus ylides through cumulated trienoates as key intermediates: a phosphine α-addition-δ-evolvement of an anion pathway.

Multicomponent reactions of phosphines, diynedioates, and aryl aldehydes have been demonstrated, providing trisubstituted furans appending reactive phosphorus ylides, through cumulated trienoates as key intermediates. The proposed trienoate intermediates, 1,5-dipolar species formed via nucleophilic α-attack of phosphines toward diynedioates (α-addition-δ-evolvement of an anion, abbreviated αAδE), undergo addition to aryl aldehydes followed by 5-endo-dig cyclization, proton transfer, and resonance to give trisubstituted furans. Furthermore, the phosphorus ylides are oxidized to α-keto ester furans and utilized as Wittig reagents.

One-pot synthesis of highly substituted polyheteroaromatic compounds by rhodium(III)-catalyzed multiple C-H activation and annulation.

A new method for the synthesis of highly substituted naphthyridine-based polyheteroaromatic compounds in high yields proceeds through rhodium(III)-catalyzed multiple C-H bond cleavage and C-C and C-N bond formation in a one-pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π-conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation-assisted ortho C-H activation, alkyne insertion, and reductive elimination, is proposed for this transformation.