A unified strategy involving visible-light-induced iminyl-radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac-[Ir(ppy)3 ] as a photoredox catalyst, oximes were converted by 1 e(-) reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give N-containing arenes. These reactions proceeded with broad range substrates at room temperature in high...

Bring to light: The first visible-light-promoted somophilic isocyanide insertion occurs using an iridium photocatalyst. This efficient synthetic approach provides a rapid entry 6-alkylated phenanthridine derivatives (see scheme). reactions proceed at room temperature in good excellent yields with broad substrate scope and under environmentally friendly conditions. As service our authors readers, this journal supporting information supplied by the authors. Such materials are peer reviewed may...

This review covers the recent literature on oxidative generation of N-centered radicals using photoredox catalysis. The concept proton-coupled electron transfer is briefly discussed. Applications such reactive in cascade processes comprising arene amidation, alkene C—C bond cleavage reactions, and remote C—H functionalization are addressed. In addition, novel reagents allowing for clean N-radical

The visible-light-promoted decarboxylation of α-imino-oxy propionic acids for the generation iminyl radicals has been accomplished through use Ir(dFCF3 ppy)2 (dtbbpy)PF6 as a photoredox catalyst. Different from homolysis and single-electron reduction oxime derivatives, this strategy provides novel catalytic cycle alkene carboimination sequence comprising N-radical generation, radical cyclization, intermolecular conjugate addition to Michael acceptor, afford various pyrroline derivatives in...

Abstract Direct CH functionalization of various enamides and enecarbamates was realized through visible‐light photoredox catalyzed reactions. Under the optimized conditions using [Ir(ppy) 2 (dtbbpy)PF 6 ] as photocatalyst in combination with Na HPO 4 , such N ‐vinylpyrrolidinone could be easily functionalized by irradiation reaction mixture overnight acetonitrile visible light. The scope respect to enamide enecarbamate substrates diethyl 2‐bromomalonate for alkylation explored, followed an...

Abstract A method for site‐specific intermolecular γ‐C(sp 3 )−H functionalization of ketones has been developed using an α‐aminoxy acid auxiliary applying photoredox catalysis. Regioselective activation inert C−H bond is achieved by 1,5‐hydrogen atom abstraction oxidatively generated iminyl radical. Tertiary and secondary C‐radicals thus formed at the γ‐position imine functionality undergo radical conjugate addition to various Michael acceptors provide, after reduction hydrolysis,...

Abstract A quinoline‐based ligand effectively promotes the palladium‐catalyzed borylation of C(sp 3 )H bonds. Primary β‐C(sp bonds in carboxylic acid derivatives as well secondary a variety carbocyclic rings, including cyclopropanes, cyclobutanes, cyclopentanes, cyclohexanes, and cycloheptanes, can thus be borylated. This directed method complements existing iridium(I)‐ rhodium(I)‐catalyzed CH reactions terms scope operational conditions.

Pd(II)-catalyzed olefination of γ-C(sp(3))-H bonds triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition the olefinated intermediates provides a variety C-2 alkylated pyrrolidines. Three pyridine- quinoline-based ligands are developed to match different classes amine substrates, demonstrating rare example ligand-enabled C(sp(3))-H reactions. The use Ns protecting group direct activation alkyl also...

Abstract A mild, practical method to prepare α‐sulfonyl and α‐trifluoromethyl ketones from readily available enol acetates sulfonyl chlorides has been developed using visible‐light photoredox catalysis. The could be used with a wide range of chlorides, gave the desired products in satisfactory excellent yields.

Radical alkynyltrifluoromethylation of alkenes with actylenic triflones has been achieved. This radical chain reaction is initiated by a catalytic amount an electron-donor–acceptor complex composed Togni's reagent and N-methylmorpholine. transformation proceeds under exceptionally mild operationally simple conditions. A variety are compatible in this protocol including aliphatic alkenes, vinyl ethers, enecarbamates, styrenes, even acrylates, providing diverse β- trifluoromethyl alkynes good...

A mechanistically new strategy has been described for the simple, practical, and environmentally friendly preparation of 6-(trifluoromethyl)phenanthridine derivatives using ionic isocyanide insertion from biphenyl Umemoto's reagent. These reactions were promoted only by inorganic base in good-to-excellent chemical yields without any external stoichiometric oxidants radical initiators.

A synthetic strategy for multi-substituted isoquinoline derivatives has been developed using visible light-promoted vinyl isocyanide insertion with diaryliodonium salts at room temperature. The methodology presented here represents the first example of synthesis via somophilic insertion.

A three-component transition-metal-free amidofluorination of unactivated alkenes and styrenes is presented. α-Amido-oxy acids are introduced as efficient easily accessible amidyl radical precursors that oxidized by a photoexcited organic sensitizer (Mes-Acr-Me) to the corresponding carboxyl radical. Sequential CO2 aldehyde/ketone fragmentation leads an N-centered adds alkene. Commercial Selectfluor used trap adduct through fluorine-atom transfer. The transformation features high...

A conceptually new strategy has been described for the mild, practical, and environmentally friendly preparation of naphthols furans using a visible-light promoted photoredox neutral approach. These reactions between accessible electron-deficient bromides commercially available alkynes could be carried out at room temperature in good-to-excellent chemical yields without any external stoichiometric oxidants.

Abstract A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac ‐[Ir(ppy) 3 ] as a photoredox catalyst, oximes were converted by 1 e − reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give N‐containing arenes. These reactions proceeded with broad range substrates at room temperature in...

A three-component 1,2-aminoarylation of vinyl ethers, enamides, ene-carbamates and thioethers by synergistic photoredox nickel catalysis is reported. 2,2,2-Trifluoroethoxy carbonyl protected α-amino-oxy acids are used as amidyl radical precursors. anti-Markovnikov addition the to alkene Ni-mediated radical/transition metal cross over lead corresponding product. The cascade, which can be conducted under practical mild conditions, features high functional group tolerance broad substrate scope....

Abstract A mild, practical and environmentally friendly strategy to prepare β‐amidovinyl sulfones has been developed based on the sulfonation of enamides or enecarbamates via visible‐light photoredox catalysis. Direct CH functionalizations under optimized conditions proceeded with a wide scope substrates remarkable selectivity give functionalized vinyl good excellent yields.

Abstract A strategy has been developed for the regiospecific synthesis of 1‐trifluoromethylisoquinoline derivatives. This is enabled by a photoredox vinyl isocyanide insertion with help Umemoto’s reagent. The methodology presented here provides an access to highly fuctionalized 1‐trifluoromethylisoquinolines regiospecifically under mild conditions in good‐to‐excellent chemical yields. detailed mechanism proposed, which supported experiments and theoretical calculations. magnified image

Abstract Two‐component Giese type radical additions are highly practical and established reactions. Herein, three‐component conjugate of unactivated alkenes to Michael acceptors reported. Amidyl radicals, oxidatively generated from α‐amido oxy acids using redox catalysis, act as the third reaction component which add alkenes. The adduct radicals engage in provide, after reduction, products an overall alkene carboamination reaction. Transformations can be conducted under mild conditions...

The conventional detection methods cannot satisfy the need for early and rapid of monkeypox virus (MPXV) infection. This is due to complicated pretreatment, time consumption, complex operation diagnostic tests. Based on surface-enhanced Raman spectroscopy (SERS), this study attempted capture characteristic fingerprints MPXV genome multiple antigenic proteins without design specific probes. minimum limit method 100 copies/mL, with good reproducibility signal-to-noise ratio. Therefore,...

A transition-metal-free radical 1,2-amidoalkynylation of unactivated alkenes is presented. α-Amido-oxy acids were used as amidyl precursors, which oxidized by an organic photoredox catalyst (4CzlPN). The electrophilic N-radicals chemoselectively reacted with various aliphatic and the adduct radicals then trapped ethynylbenziodoxolone (EBX) reagents to eventually provide amidoalkynylation products. These transformations, conducted under practical mild conditions, showed high functional group...

Abstract The visible‐light‐promoted decarboxylation of α‐imino‐oxy propionic acids for the generation iminyl radicals has been accomplished through use Ir(dFCF 3 ppy) 2 (dtbbpy)PF 6 as a photoredox catalyst. Different from homolysis and single‐electron reduction oxime derivatives, this strategy provides novel catalytic cycle alkene carboimination sequence comprising N‐radical generation, radical cyclization, intermolecular conjugate addition to Michael acceptor, afford various pyrroline...

A practical approach for the synthesis of tetracyclic pyrroloquinazolines using photoredox strategy has been developed. The visible-light-promoted intramolecular single-electron-transfer process between photocatalyst and N-(2-iodobenzyl)-N-acylcyanamides is considered to be involved in this transformation. Targeted pyrroloquinazoline derivatives (15 examples) are presented good isolated yields (30%-88%).