Search

A tunable method for the selective preparation of p -aminophenol and tertiary amines from a secondary amine and cyclohexenone has been described. Nonaromatic cyclohexenones were used as an aryl source. The desired tertiary amine products were generated when using I 2 as the catalyst. This approach yields single-site-selective p -aminophenol without using I 2 , and the 18 O labeling experiments demonstrated that hydroxyl oxygen originates from O 2 .

A novel and unique approach for the construction of polysubstituted pyrimido[4,5- b ]indoles from 2-(indol-3-yl)naphthoquinones and benzamidines is described. Our strategy, promoted by an inorganic base, involves the ring opening and recyclization of naphthoquinone and produces three nitrogen heterocyclic rings via multiple C-N bond formations in one pot under transition-metal-free conditions.

A novel visible-light-driven photoredox-catalyzed cascade bicyclization of 1,7-enynes with aqueous sulfoxonium ylides is reported. The reaction is highly chemoselective with three new C-C bonds, two new rings, and an all-carbon quaternary stereocenter constructed in a one-pot fashion. This mild protocol features a remarkably broad substrate scope with good functional group tolerance, providing a general and practical approach to access various cyclopenta[ c ]quinolines.

The diversity of catalytic products determines the difficulty of selective product modulation, which usually relies on adjusting the catalyst and reaction conditions to obtain different main products selectively. Herein, we synthesized D-π-A-D conjugated organic polymers (TH-COP) using cyclotriphosphonitrile, alkyne, 2H-benzimidazole, and sulfur units as electron donors, π bridges, electron acceptors, and electron donors, respectively. TH-COP exhibited excellent photoinduced carrier separation and redox ability under different visible light wavelengths, and the main products of its CO 2 reduction are CH 4 (1000.0 μmol g -1 ) and CO (837.0 μmol g -1 ) under 400-420 nm and 420-560 nm, respectively. In addition, TH-COP could completely convert phenylmethyl sulfide to methyl phenyl sulfone at 400-420 nm and diphenyl disulfide at 480-485 nm in yields up to 95 %. This study presents a novel strategy for the targeted fabrication of various main products using conjugated polymers by simply changing the wavelength range of visible light., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Herein, we have developed a complementary entry to enable hydroheteroarylation of alkenes involving basically photoredox dearomatizative heterocyclic carbon radical formation through acid-coupled electron transfer followed by Giese addition. While protonic solvent and thiophenol additive enabled two molecular hydroheteroarylations of alkenes, the nonproton environment with BF 3 altered the chemoselectivity over cascade hydroheteroarylation of alkenes by radical addition of heteroaromatics with two molecular alkenes. This chemoselectivity can be mechanistically attributed to the dynamically favored hydrogen atom transfer via the cyclic transition state.

A convenient protocol for synthesis of unsymmetrical 2-methylpyridines from acetyl ketones, ammonium salts and tertiary amines is described. The construction of two C-C bonds and two C-N bonds via [2 + 2 + 1 + 1] four-component domino cyclization reaction is achieved using Cu(OTf) as catalyst in one pot. This cyclization reaction shows good selectivity and produces multisubstituted 2-methylpyridine derivatives in good yields with various functional groups.

The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use of high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems for defluoroalkylation of readily available trifluoromethylarenes through selective C-F cleavage to deliver gem-difluoromethyl radicals which proceed through reductive addition to both electron-donating and withdrawing alkenes under transition-metal free conditions. Mechanistic studies reveal that thiol serves as both photocatalyst and HAT reagent under visible light irradiation. This synergistic photocatalysis and HAT catalysis protocol exhibits ample and salient features such as high chemo- and regioselectivity, broad substrate scope, amenable gram-scale synthesis and late-stage modification of bioactive molecules.

Disulfide bonds, especially unsymmetric disulfide bonds, have important applications in bioactivity and drug molecules, but the synthesis of unsymmetric disulfide bonds remains challenging due to efficiency and selectivity issues. Herein, this work utilizes anthraquinone (AQ) and cyclictriphosphonononitrile through a nucleophilic substitution reaction to synthesize an organic polymer (ANTH-AMI) that incorporates an ortho-polyquinone (o-polyquinone) redox center. The anthraquinone molecule functions as a redox center, capable of accepting photoinduced electrons and subsequently transferring them to initiate an electron-coupled hydrogenation reaction (AQ to AQH). Moreover, the proximity of the o-polyquinone redox sites facilitates the catalysis of unsymmetric disulfide bond formation. Consequently, the ANTH-AMI photocatalysts demonstrate exceptional yields (up to 82 %), substrate versatility, cycling stability, and scalable preparation in promoting unsymmetric coupling reactions of thiol. This work offers a solution for designing organic polymer photocatalysts with adjacent multiple redox centers for cross-coupling reactions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

A visible-light-induced photoredox three-component carbocyclization reaction of 1,7-enynes with sulfoxonium ylides and water is reported. The protocol provides a facile entry to structurally valuable highly functionalized cyclopenta[ c ]quinoline scaffolds in a highly chemoselective and stereoselective manner. Salient features of this method include facile redox-neutral conditions, no requirement of base or other additive, and good functional-group tolerance.

A copper-catalyzed three-component coupling reaction of styrene oxide, aryl iodide, and carbon disulfide for the construction of β-hydroxysulfides has been developed. In this process, readily available CS 2 was used as the sulfur source to construct C-S bonds for the synthesis of phenyl-β-hydroxysulfides and (benzo[ d ]thiazol)-β-hydroxysulfides. This process features mild reaction conditions, simple operation, and wide substrate scope (>50 examples).

Pyrrolo[1,2- a ]indoles are structurally important scaffolds in many natural products and bioactive compounds. Herein, we report a novel synthetic method for pyrrolo[1,2- a ]indole derivatives through visible-light-induced cascade dearomatizative cyclization of indoles with external nucleophiles. Moderate yields, good diastereoselectivities, and excellent regioselectivities were generally observed with the resultant indole-fused polycyclic compounds.

A selective three-component 1,2-sulfonyl etherification of aryl 1,3-dienes enabled by copper catalysis to afford biologically interesting alkenyl 1,2-sulfone ether derivatives through C-S and C-O bond formation is described. The protocol proceeds with the sulfonyl chloride and alcohols under simple, mild, and base-free conditions, providing a straightforward route to sulfonylated allyl ether compounds with broad functional group tolerance and excellent chemo- and regioselectivity. Mechanistic studies indicate that the selective alkene difunctionalization includes a key copper-mediated single-electron transfer process.

Herein, we introduce a tetralone-mediated photocyclization method of N -arylacrylamides. The protocol proceeds smoothly to deliver a diverse set of 3,4-dihydroquinolinones in moderate to good yields with excellent functional group compatibility and readily allows for late-stage modifications of a number of complex drug molecules. Mechanistic studies reveal that the present systems with ultraviolet light irradiation enable the cyclization via energy transfer and exclusive 1,3-hydrogen shift.

The photoredox/PPh 3 -mediated cyclization of 2-isocyanobiaryls has been developed. A substantial range of functional-group-rich phenanthridine derivatives were synthesized at room temperature in a highly selective and atom-economic manner. Mechanistic studies suggested that the cyclization process is probably mediated both by Ph 3 P radical cation with key 1,2-hydride transfer and hydrogen atom generated through O-H bond homolytic cleavage of Ph 3 P-OH radical intermediate.

A three-component 1,4-alkylarylation of 1,3-enynes with organic halides through the combination of nickel and photoredox catalysis has been established, providing a novel and modular approach for the assembly of tetrasubstituted allenes. This reductive cascade cross-electrophile reaction obviates the need for air-sensitive organometallic reagents and stoichiometric metallic reductants. A diverse range of functional groups are very compatible under mild reaction conditions and give satisfactory yields. Moreover, a reasonable mechanism is presented according to a series of control experiments.

2-Azidoimines are versatile precursors to value-added vicinal unsymmetrical diamines, which are among the most common motifs in biologically active compounds. Herein, we report their operationally simple synthesis through a highly regioselective intermolecular azidoamination of olefins under metal-free conditions. The approach proceeded through azide and iminyl, two differentiated N -centered radicals. The synthetic potential of the protocols was further established via the condensation/amination sequential cascade and chemoselective, orthogonal transformations to access vicinal primary diamines.

A facile and practical approach for the preparation of substituted pyrimidines from ketones, NH 4 OAc, and N , N -dimethylformamide dimethyl acetal has been described. This NH 4 I-promoted three-component tandem reaction affords a broad range of substituted pyrimidines in acceptable yields under metal- and solvent-free conditions. The present methodology features the advantages of simple and easily available starting materials, metal- and solvent-free conditions, a broad substrate scope with good functional group tolerance, and gram-scale synthesis.

An environmentally benign multicomponent strategy for the amidosulfenylation of alkenes for the synthesis of β-succinimide sulfides is disclosed. In this process, common disulfides smoothly act as a sulfur-based source, and N -iodosuccinimide (NIS) is used not only as a free radical initiator but also as an N -nucleophile. A broad range of functional groups are tolerated in this reaction system.

A novel and selective synthesis of polycyclic fused maleimides from easily available raw materials under metal-free conditions is presented. This cascade protocol involves self-condensation of cyclohexanones, followed by Diels-Alder reaction with maleimides, intramolecular dehydration, and selective dehydroaromatization in a one-pot fashion, affording maleimide-fused 9,10-phenanthrenes and their analogues in satisfactory yields. Notably, iodide reagents play a critical role in switching the selectivity toward full or partial dehydrogenation compounds.

Herein, we have developed an atom- and step-economic three-component cascade reaction that enables a modular platform for the synthesis of pyrrolo[2,3- c ]quinoline compounds through ring-expansion/cyclization by way of novel N1-C2 cleavage of indoles. The metal-free catalytic system exhibits a broad functional group tolerance.

The knowledge of physical mechanism of microwave generation in coaxial gyromagnetic nonlinear transmission lines (GNLTLs) is not complete up until now, especially the action of spinwave excitation during this process. In this paper, control experiments on different groups of GNLTLs with a single variable of NiZn ferrite material spinwave linewidth ΔHk are proposed as an indirect way to demonstrate this microscopic process. Comparative analyses of different groups of GNLTL experimental results are conducted to clarify the existence and effect of spinwave excitation. Theoretical treatment of conditions of spinwave excitation in GNLTLs is derived to explain the experimental results. It is illustrated that spinwave can be excited when the synchronism condition between the working frequency of GNLTL and the spinwave frequency spectrum is satisfied. The unstable spinwave excitation will consume the RF energy of GNLTLs heavily and cause a rapid decrease in RF oscillation., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

A visible-light-induced cascade arylazidation of activated alkenes with trimethylsilyl azide (TMSN 3 ) has been developed. Mechanistic investigations reveal that the single electron transfer (SET) of TMSN 3 with the excited photocatalyst was involved in the initial step, followed by radical addition/aryl migration/desulfonylation to furnish valuable α-aryl-β-azido amides and azidated oxindoles under mild conditions, which are versatile building blocks in organic synthesis. With simple treatment, the obtained arylazidated products were further converted to valuable β-amino amide and 1,2,3-triazole derivatives.

Herein, we develop a Rh(III)-catalyzed intermolecular regioselective dearomative spirocyclization of 2-aryl-3-nitrosoindoles with alkynes, featuring the redox-neutral and atom-economic construction of spiroindoline-3-one oximes bearing a C2 spirocyclic quaternary carbon center under mild conditions. Both aryl alkyl alkynes and 1,3-diynes generally proceeded smoothly in the reaction with moderate to good regioselectivities. DFT calculations provided in-depth insights into the reaction mechanism and disclosed the origins of the regioselectivities.

A three-component strategy was developed for 3-phenyl-9 H -imidazo[1,5- a ]indol-9-one preparation from indole-2-carboxaldehydes, aromatic aldehydes, and ammonium acetate under copper catalysis conditions. In this process, a new five-membered ring was formed and the C3 position in the indole substrate was selectively oxidized into a ketone skeleton using oxygen as the sole oxidant and ammonium acetate as the nitrogen source. Furthermore, same products also could be achieved from indole-2-carboxaldehydes and benzyl amines under similar reaction conditions.

A visible-light induced direct C(sp 3 )-H functionalization of alkylarenes with trifluoromethyl ketones has been reported to access valuable benzyl-substituted trifluoromethyl alcohols in a stoichiometric manner. Readily available petroleum-derived alkylarenes are employed as latent benzylation reagents. With a bromine radical as the hydrogen atom transfer reagent, primary, secondary, and tertiary benzyl C-H bonds are suitable coupling partners. Additionally, the late-stage modification of bioactive molecules highlights the potential application of this approach.

A highly site-selective trifluoromethylaminoxylation of activated and unactivated olefins was reported under metal-free conditions. The method provides direct access to diverse β-trifluoromethyl trisubstituted hydroxylamines, tertiary alcohols, isoxazolines, isoxazolidines, and amino alcohols. The SET process between hydroxylamine and the hypervalent iodine-CF 3 reagent is proposed to produce two free radicals for the regio- and diastereoselective addition to alkenes. The synthetic potential of the protocol was established via the late-stage functionalization of the products and a series of postreaction modifications.

The significance of chiral α-tertiary amines in medicinal chemistry and drug development has been unquestionably established in the last few decades. α-Tertiary amines are attractive structural motifs for natural products, bioactive molecules and pharmaceuticals and are preclinical candidates. Their syntheses have been the focus of intensive research, and the development of new methods has continued to attract more and more attention. In this review, we present the progress in the last decade in the development of synthetic methods for the assembly of chiral ATAs via transition-metal catalysis. To date, the effective approaches in this area could be categorized into three strategies: enantioselective direct and indirect Mannich addition to ketimines; umpolung asymmetric alkylation of imine derivatives; and asymmetric C-N cross-coupling of tertiary alkyl electrophiles. Several related developing strategies for the synthesis of ATAs, such as hydroamination of alkenes, HAT amination approaches and the C-C coupling of α-aminoalkyl fragments, are also described in this article. These strategies have emerged as attractive C-C and C-N bond-forming protocols for enantioselective construction of chiral α-tertiary amines, and to some extent are complementary to each other, showing the prospect of application in medicinal chemistry and chemical biology.

A facile method for the rapid synthesis of benzoacridines has been described. This protocol promoted by p-toluenesulfonic acid starts from aromatic aldehydes and N-phenyl naphthylamines, affording a variety of benzoacridines in 30-90 % yields under metal-free conditions. The present approach involves a cascade of condensation, Friedel-Crafts alkylation, annulation and dehydroaromatization in one pot., (© 2023 Wiley-VHCA AG, Zurich, Switzerland.)

A metal-free method for the construction of 2-substituted quinolines and benzo[ f ]quinolines from aromatic amines, aldehydes, and tertiary amines has been demonstrated. Cheap and readily available tertiary amines acted as the vinyl source. A new pyridine ring was selectively formed via [4 + 2] condensation that was promoted by ammonium salt under neutral conditions and an oxygen atmosphere. This strategy provided a new route for the preparation of various quinoline derivatives with different substituents at the pyridine ring, which provides the possibility of further modification.

Herein, we report a novel visible light-induced photocatalytic system that enables intramolecular hydroarylation of unactivated alkenes. Thiosulfonate compounds were found to be the key radical precursor that mediates the Minisci-type intramolecular cyclization reaction. Under the optimal reaction conditions, a wide range of pyridyquinazolinone and pyrroloquinazolinone products were obtained in moderate to good yields.

An iodine-containing reagent promoted three-component method for the selective synthesis of phenothiazines and bis-phenothiazines has been developed. The present protocol starts from simple and easily available cyclohexanones, elemental sulfur, and inorganic ammonium salts, selectively producing phenothiazines and bis-phenothiazines in satisfactory yields under aerobic conditions. This method has the advantages of simple and readily available starting materials and metal-free conditions, affording a facile and practical approach for the preparation of phenothiazines and bis-phenothiazines.

The visible-light-induced photoredox carbon radical formation from aqueous sulfoxonium ylides has been demonstrated for the first time. While direct reduction of sulfoxonium ylides by H 2 O efficiently generates the corresponding hydrocarbon compounds, the use of additional alkenes as radical acceptors alters the chemical reactivity to achieve alkene carboarylation of N -arylacrylamides. Mechanistic studies reveal two different reaction pathways involved in the carbon radical formation from aqueous sulfoxonium ylides resulting in reduction to release dimethyl sulfone and carboarylation to form DMSO.

A CuBr 2 -catalyzed annulation of 2-bromo- N -arylbenzimidamide with selenium/sulfur powder for the synthesis of benzo[ d ]isoselenazole and benzo[ d ]isothiazole in generally good yields was investigated. This synthetic strategy features good substrate scope and functional group tolerance. Furthermore, the corresponding products could be converted into N -aryl indoles via rhodium III -catalyzed ortho C-H activation of the N -phenyl ring, providing an efficient approach for axial aromatic molecules.

A four-component synthesis of tetrasubstituted pyrroles was developed under metal-free conditions. The pyrrole ring was formed in one pot through [2 + 1 + 1 + 1] condensation using ammonium salt as the nitrogen source. In this strategy, 1,4-naphthoquinones and maleimides were used as the versatile C2 fragments to provide substituted benzo[ f ]isoindole-4,9-diones and pyrrolo[3,4- c ]pyrrole-1,3-diones, respectively. This work is highlighted by using ammonium salt as the nitrogen source, readily available starting materials and multibond formation (two C-C and two C-N bonds) in a single operation.

Photocatalytic CO 2 reduction and H 2 production are a competitive reaction, and existing active sites cannot take into account the simultaneous gas-solid and liquid-solid reaction processes. Hence, a metallic aerogel (CuAg 2.5 ) with dual active sites was constructed via straightforward in-situ reduction process. CuAg 2.5 aerosol has larger porosity and CO 2 adsorption capacity, which enables H 2 O and CO 2 to fully contact it. The CuAg 2.5 can also construct the cooperative dual active sites, which can conduct CO 2 reduction reaction on Ag surface and proton reduction reaction on Cu surface, respectively, thereby efficiently guiding the rapid migration of photogenerated carriers. The yields of CO (18533 µmol g -1 ) and H 2 (20340 µmol g -1 ) for CuAg 2.5 are much higher than those of single metals. The ratio of CO and H 2 can also regulated via changing the ratio of Ag and Cu. This work gives new insights into the fabrication of unique high-efficiency plasmonic photocatalysts., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

The effective photoredox-mediated oxidative thiolation and cyclization of N -arylacrylamides with thiols leads to biologically interesting 3-thionated oxindoles through C-S and C-C bond formation. This process represents a straightforward reaction that starts from non-prefunctionalized thiolating reagents. Mechanistic studies demonstrated that the TBHP serves as a key radical initiator with visible-light catalysis.

A Pd-catalyzed C-O cross-coupling of O -acyl hydroxylamines and tertiary or secondary alkyl electrophiles was reported without the cleavage of the rather fragile N-O bond. The described strategy provides direct access to congested N , N , O -trisubstituted hydroxylamines bearing an α-quaternary carbon center under mild conditions in high yields and features exclusively chemoselective C-O bond formation, a broad substrate scope, and excellent functional group tolerance. The synthetic potential of the cross-coupling was established via pharmaceuticals derivatizations and a series of postcatalytic modifications.

We have reported a metal-free protocol for the synthesis of indenoquinolinones and 2-substituted quinolines via [4 + 2] cycloaddition reaction using readily available 2-aminobenzaldehydes and ketones as starting materials. Different quinoline derivatives can be selectively synthesized by changing the type of ketones. O 2 and dimethyl sulfoxide (DMSO) as co-oxidants play an important role in the synthesis of indenoquinolinones. This condensation/oxidation strategy involves the formation of C-N, C-C, and C-O bonds, with the advantages of high yields and a broad substrate range.

Herein, we describe a novel visible-light-induced protocol for hydrogen-borrowing reduction/dehydrogenation aromatization/cyclization of nitroarenes by energy transfer. The present protocol does not require additional oxidants, hydrogen acceptors, and hydrogen evolution metal catalysts. The mechanistic studies demonstrated that the hydrogen-borrowing reduction/dehydrogenative aromatization process was initiated by the formation of active singlet species through efficient energy transfer of excited Ir[dF(CF 3 )ppy] 2 (dtbpy)PF 6 to nitroarenes.

A three-starting-material four-component reaction strategy is described to construct thienopyrrolediones (TPDs) from the simplest raw materials, elemental sulfur, aldehydes, and β-ketoamides, under transition metal free conditions. Compared with traditional multistep reaction sequences, this process is simple, efficient, environmentally friendly, and atom-economic and has laid the foundation for further development of an easily synthesized TPD unit.

A novel strategy for the preparation of functional carbazoles through NaI-catalyzed formal [4 + 2] annulation of 2-(indol-3-yl)cyclohexanones and alkynes/alkenes has been developed. The present approach started from easily available raw materials and provided a variety of tetrahydrobenzo[ c ]carbazolones in satisfactory yields under metal- and solvent-free conditions. Furthermore, the products could be further transformed into structurally valuable carbazole-based conjugated derivatives.

Photoredox neutral decarboxylative hydroxyalkylations of heteroarenes with α-keto acids under mild conditions are described. Stable and readily available α-keto acids were employed as hydroxyalkylating reagents with only CO 2 released as the byproduct. A range of aromatic and aliphatic α-keto acids were successfully converted into hydroxyalkylated products with various heteroarenes. This transformation proceeded through a decarboxylation/Minisci addition/SCS sequence, generating a variety of valuable hydroxyalkylated heteroarenes.

The C-S bond formation from aryl halides and thiols has been well established under various catalytic systems. In this work, user-friendly sulfinates have been exploited as an efficient sulfenylating reagent in the C-S couplings through visible-light-induced photo/nickel dual catalysis under base- and external reductant-free conditions. A large number of aryl sulfide products were accessed with high selectivity and high tolerance of various functionalities.

A mild two-step synthetic approach for the preparation of structurally valuable indolo[3',2':4,5]pyrrolo[3,2,1- kl ]phenothiazines has been developed. In this work, cyclohexanone was used as the key bridge to connect the indole and phenothiazine frameworks to construct a structurally valuable indole-fused derivative. The present protocol achieved the cascade construction of multiple C-hetero bonds, affording a convenient approach access to hexacyclic-fused system that contained both indole and phenothiazine, two privileged skeletons.

The activity of photocatalytic CO 2 conversion to carbon-containing products is determined by the adsorption and activation of CO 2 molecules on the surface of catalyst. Here, iron doped porous CeO 2 with oxygen vacancy (PFeCe) was prepared by one-step combustion method. The amount of CO 2 adsorbed via using the porous structure has been significantly increased in the case of a relatively small specific surface area and CO 2 molecules are more easily captured and undergo a reduction reaction with photoinduced carriers. In addition, oxygen vacancies are formed in the iron doped CeO 2 lattice as the active sites for CO 2 reduction, which can form strong interactions with CO 2 molecules, thereby effectively activating CO 2 molecules. The reduction products of CO 2 over PFeCe composite are CO and CH 4 , which is approximately 9.0 and 7.7 folds than that of CeO 2 . This work offers insights for the construction of efficient ceria-based photocatalysts to further achieve robust solar CO 2 conversion., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

A Cu-catalyzed three-component N -alkylation coupling reaction of N-heteroarenes with methyl ketones and DMPA as a carbon source has been developed. Using methyl ketones as alkylation reagents and DMPA ( N , N '-dimethylpropionamide) as a carbon source, the reaction proceeded smoothly under the Cu-based oxidative system and led to a series of functionalized N-heterocycles including 4-quinazolinones, triazoles and pyrazoles.

Metal- and additive-free photoredox cyclization of N -arylacrylamides is herein reported that provides a concise access to the formation of dihydroquinolinones. In this protocol, sustainable visible light was used as the energy source, and the organic light-emitting molecule 4CzIPN served as the efficient photocatalyst. This reaction system features exclusive 6- endo-trig cyclization selectivity with a generally good yield of a range of functionalized dihydroquinolinones and dihydrobenzoquinolinones. Mechanistical studies reveal the feasibility of both 1,3-H shift and intersystem crossing of the diradical intermediate.

We have introduced a metal-free facile access for the thiolation/aromatization of cyclohexanones with thiophenols to the corresponding aryl sulfides. The dehydroaromatic reaction of non-aromatic cyclohexanones proceeded smoothly using oxygen as a green oxidant.

By using a low CO 2 concentration as a C1 source, the design of a plasmonic catalyst that can effectively photocatalytic CO 2 reduction is of great significance for sustainable and ecological development. Herein, the space confinement effect and liquid environment of the molten salt result in uniform hollow structure, while the strong aggressive force furnished via using molten salt enhances the formation of line defects. This special structure can not only provide a large number of active sites but also greatly accelerate the transport of photoinduced charge carriers. The hollow copper ball with line defects (CCu) shows excellent photocatalytic activity with pure water (1028.57 μmol g -1 ), and it also shows good catalytic activity even under ultra-low CO 2 content, which far exceeds the catalytic activity of most semiconductor-based catalysts. This work is designed to simultaneously construct line defect and hollow structure in plasmatic metal nanoparticles for efficient photocatalytic CO 2 reduction., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

A convenient and efficient strategy for the synthesis of dibenzoxazepinamines and dibenzothiazepinamines has been developed. This three-component approach started from 2-nitrobenzaldehydes, 2-aminophenols, and methoxyammonium chlorides under metal-free conditions. The protocol has the advantages of readily available starting materials, simple and facile conditions, gram-scale synthesis, and broad substrate scope, providing an efficient and practical strategy for the preparation of potential drug-active dibenzoxazepinamines and dibenzothiazepinamines in one pot.