Hydroazidation of trifluoromethyl alkenes with trimethylsilyl azide enabled by organic photoredox catalysis.

Herein, we report an organic photoredox-catalyzed hydroazidation of trifluoromethyl alkenes with user-friendly trimethylsilyl azide (TMSN3), enabling a direct access to a broad range of valuable ß-CF3-azides with exclusive selectivity under mild reaction conditions. The synthetic utility of this reaction was demonstrated by the late-stage modification of complex drug derivatives, scale-up of the reaction and diverse further derivatizations of the ß-CF3-azide product.

Photoredox/Bismuth Relay Catalysis Enabling Reductive Alkylation of Nitroarenes with Aldehydes.

The effective transition metal-free photoredox/bismuth dual catalytic reductive dialkylation of nitroarenes with benzaldehydes has been reported. The nitroarene redution through visible light-driven photoredox catalysis was integrated with subsequent reductive dialkylation of anilines under bismuth catalysis to enable the cascade reductive alkylation of nitroarenes with carbonyls. Salient features of this relay catalysis system include mild reaction conditions, no requirement for transition metal catalysts, easy handling, step-economy, and high selectivity.

Copper-Catalyzed 1,2-Sulfonyletherification of 1,3-Dienes.

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.

Accessing pyrrolo[1,2-a]indole derivatives via visible-light-induced dearomatizative cyclization of indoles.

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.

Accessing 3,4-Dihydroquinolinone from N-Arylacrylamides via Tetralone-Mediated Energy Transfer and 1,3-Hydrogen Shift.

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.

Photoredox Enabled Defluorinative Benzylation of Trifluoromethyl Alkenes with Alkylarenes.

Herein, we report a photoredox enabled defluorinative benzylation of trifluoromethyl alkenes with readily available alkylarenes, which provides convenient access to a series of structurally valuable benzylated gem-difluoroalkenes under mild reaction conditions. The synthetic value of this protocol has been demonstrated by the transformations of several substrates bearing drug moieties, gram-scale reactions, and various further derivatizations of the gem-difluoroalkene products. The preliminary mechanistic investigations suggest a reaction pathway with rate-determining benzyl C-H bond cleavage of toluene followed by benzylic radical formation.

Redox-Neutral Cyclization of 2-Isocyanobiaryls through Photoredox/PPh3 Dual Catalysis.

The photoredox/PPh3-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 Ph3P radical cation with key 1,2-hydride transfer and hydrogen atom generated through O-H bond homolytic cleavage of Ph3P-OH radical intermediate.

Catalyst- and additive-free cascade radical addition/cyclization of N-arylacrylamides with trifluoropyruvates.

Herein, we introduce a photocatalyst- and additive-free method for the preparation of valuable 3,3-disubstituted oxindoles bearing trifluoromethyl alcohol moieties from readily available acrylamides and cheap trifluoropyruvates. The excited trifluoropyruvates under ultraviolet-light irradiation react efficiently with acrylamides delivering a variety of trifluoromethyl oxindoles with broad functional group tolerance and moderate to good yields. This protocol features mild reaction conditions, simple operation and ready scalability.

Three-Component Ring-Expansion Reaction of Indoles Leading to Synthesis of Pyrrolo[2,3-c]quinolines.

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.

Visible-Light-Induced Cascade Arylazidation of Activated Alkenes with Trimethylsilyl Azide.

A visible-light-induced cascade arylazidation of activated alkenes with trimethylsilyl azide (TMSN3) has been developed. Mechanistic investigations reveal that the single electron transfer (SET) of TMSN3 with the excited photocatalyst was involved in the initial step, followed by radical addition/aryl migration/desulfonylation to furnish valuable α-aryl-ß-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 ß-amino amide and 1,2,3-triazole derivatives.

Visible-Light-Induced Stoichiometric Coupling of Alkylarenes and Trifluoromethyl Ketones.

A visible-light induced direct C(sp3)-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.

Recent Advances in Molecule Synthesis Involving C-C Bond Cleavage of Ketoxime Esters.

The synthetic strategies of oxime derivatives participating in radical-type reactions have been rapidly developed in the last few decades. Among them, the N-O bond cleavage of oxime esters leading to formation of nitrogen-centered radicals triggers adjacent C-C bond cleavage to produce carbon-centered free radicals, which has been virtually used in organic synthesis in recent years. Herein, we summarized the radical reactions involving oxime N-O bond and C-C bond cleavage through this special reaction form, including those from acyl oxime ester derivatives and cyclic ketoxime ester derivatives. These contents were systematically classified according to different reaction types. In this review, the free radical reactions involving acyl oxime esters and cyclic ketoxime esters after 2021 were included, with emphasis on the substrate scope and reaction mechanism.

Radical-mediated photoredox hydroarylation with thiosulfonate.

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.

Visible-Light-Mediated Photoredox Carbon Radical Formation from Aqueous Sulfoxonium Ylides.

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 H2O 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.

TBHP-mediated photochemical coupling/cyclization of N-arylacrylamides with thiols.

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.

Progress in C-C and C-Heteroatom Bonds Construction Using Alcohols as Acyl Precursors.

Acyl moiety is a common structural unit in organic molecules, thus acylation methods have been widely explored to construct various functional compounds. While the traditional Friedel-Crafts acylation processes work to allow viable construction of arylketones under harsh acid conditions, recent progress on developing acylation methods focused on the new reactivity discovery by exploiting versatile and easily accessible acylating reagents. Of them, alcohols are cheap, have low toxicity, and are naturally abundant feedstocks; thus, they were recently used as ideal acyl precursors in molecule synthesis for ketones, esters, amides, etc. In this review, we display and discuss recent advances in employing alcohols as unusual acyl sources to form C-C and C-heteroatom bonds, with emphasis on the substrate scope, limitations, and mechanism.

Hydrogen-Borrowing Reduction/Dehydrogenative Aromatization of Nitroarenes through Visible-Light-Induced Energy Transfer: An Entry to Pyrimidoindazoles and Carbazoles.

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(CF3)ppy]2(dtbpy)PF6 to nitroarenes.

Visible-Light-Induced Decarboxylative Alkylation/Ring Opening and Esterification of Vinylcyclopropanes.

A visible-light-induced four-component reaction of vinylcyclopropanes, N-(acyloxy)phthalimide esters, N,N-dimethylformamide (DMF), and H2O through an oxidative ring opening of cyclopropane is presented. This procedure provides a new and effective way to construct formate esters. DMF is employed as both a solvent and the source of CHO. This difunctionalization of vinylcyclopropanes shows good functional group tolerance under room temperature. A radical pathway is involved, and carbonyl oxygen of ester originated from water in this transformation.

Phase Separation Induced Binary Core-Shell Alloy Nanoparticles Embedded in Carbon Sheets for Magnesium Storage.

Magnesium-ion batteries (MIBs) have aroused widespread interest in large-scale applications due to their low cost, high volumetric capacity, and safety. However, magnesium (Mg) metals are incompatible with conventional electrolytes, making it difficult to plate and strip reversibly. Therefore, developing novel Mg2+ host anodes remains a huge challenge. Herein, we present a rational design and fabrication of binary Bi@Sn alloy nanoparticles embedded in carbon sheets (Bi@Sn-C) as a superior anode for MIBs employing phase separation during the annealing of bimetallic MOFs. The Bi@Sn-C simultaneously integrates the nanostructure design and multi-element coordination strategies which is favorable to improve the overall structural stability and Mg2+ diffusion kinetics. Benefiting from the aforementioned features, the Bi@Sn-C electrodes deliver good cycling stability of 214 mA h g-1 at 100 mA g-1 after 100 cycles and rate capability with 200 mA h g-1 at 500 mA g-1. And when using all-phenyl complex with lithium chloride (LiCl-APC) dual-salt electrolyte, the electrochemical performance of Bi@Sn-C is further optimized and shows enhanced rate performance (238 mA h g-1 at 500 mA g-1) and reversible capacity (308 mA h g-1 at 100 mA g-1 after 100 cycles). This novel strategy holds great promise for designing efficient alloy electrode materials for MIBs.

Deoxygenative C-S Bond Coupling with Sulfinates via Nickel/Photoredox Dual Catalysis.

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.