A photoinduced, phosphoranyl radical-mediated protocol for the direct N–O cleavage of strained cycloketone oximes via a polar/SET crossover process was developed first time. This visible-light-driven activation mode oxime offers beneficial features such as streamlined synthetic and versatile photochemical reactivities. Consequently, alkenes α-trifluoromethyl with varied electronic structural acted competent radical receptors in this protocol, enabling facile accesses to range elongated cyano...

The chiral allylic sulfonylated group is a unique structural motif embedded in range of natural products and pharmaceuticals. Notably, the synthesis structurally diverse derivatives via alkylsulfonylation 1,3-dienes remains underexplored because its inherent challenges stereocontrol regioselectivity. Herein, photoinduced, palladium-catalyzed enantioselective 1,2-alkylsulfonylation conjugated described. A wide variety alkyl bromides, 1,3-dienes, sodium sulfinates could be facilely coupled to...

A facile and efficient synthetic strategy to 3-((trifluoromethyl)thio)-4H-chromen-4-one was developed. AgSCF3 trichloroisocyanuric acid were employed here generate active electrophilic trifluoromethylthio species in situ. This reaction could proceed under mild conditions a short time be insensitive air moisture.

A photoinduced SET process enables the direct B-H bond activation of NHC-boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this reaction simply takes advantage beneficial redox potentials NHC-boranes, thus obviating need for extra radical initiators. The resulting NHC-boryl was used borylation a wide range α-trifluoromethylalkenes and alkenes with diverse electronic structural features, providing facile access highly functionalized borylated molecules. Labeling...

A practical and straightforward synthetic route to construct a variety of 3-CF2/CF3-containing chromones via photoredox catalysis was developed. This novel protocol features visible-light-induced radical-triggered tandem cyclization.

A metal-free photosensitized protocol for regioselective diamination of alkene feedstocks over a single step was developed based on the rationally designed bifunctional reagent, thus affording range differentially protected 1,2-diamines in moderate to high yields. Mechanistic studies reveal that reaction is initiated with triplet-triplet energy transfer between thioxanthone catalyst and followed by fragmentation simultaneously generate long-lived iminyl radical transient amidyl radical. The...

A highly modular 1,4-difunctionalization of 1,3-dienes with bromodifluoroacetamides and sulfinates/amines through a photoinduced palladium-catalyzed radical relay process is described herein. This developed protocol offers facile general route to access variety value-added CF2-incorporated alkenes in moderate good yields. The versatility flexibility this approach have been well illustrated by readily accessible starting materials, synthetic convenience, wide functional group compatibility.

A metal-free photosensitized three-component reaction of oxime esters, alkenes, and DABCO·(SO2)2 was developed. This protocol could accommodate a wide substrate scope, including activated unactivated alkenes aryl aliphatic carboxylic acid delivering broad range β-amino sulfones in moderate to high yields. The insertion SO2 as linker moiety allows the manipulation functionality process, expanding utility esters bifunctional reagents.

Herein, we disclose a facile and versatile trifluoromethylimination of alkene with rationally designed N-(diphenylmethylene)-1,1,1-trifluoromethanesulfonamide as bench-stable readily accessible carboamination reagent. Enabled by an energy transfer (EnT) process, array alkenes were able to be facilely CF3-iminated under metal-free photocatalytic conditions. The mild reaction conditions good functional group compatibility render this protocol highly valuable for the difunctionalization olefins...

A facile and diversified synthesis of functionalized CF2-containing benzoxepine derivatives via photoredox catalysis was achieved in this work. This novel protocol features broad substrate scope, mild reaction conditions, operational simplicity, easy scale-up, versatile derivatization, which would facilitate its practical applications the construction valuable synthetically challenging heterocycles.

The first photoredox-catalyzed defluoroborylation of polyfluoroarenes with NHC-BH3 has been facilely achieved at room temperature via a single-electron-transfer (SET)/radical addition pathway. This new strategy makes full use the advantage photoredox catalysis to generate key boryl radical direct activation B-H bond. Good functional group tolerance and high regioselectivity offer this protocol incomparable advantages in preparing wide array valuable polyfluoroarylboron compounds. Moreover,...

Reported herein is a visible-light-induced sulfonation of α-trifluoromethylstyrenes with sodium sulfinates, which provides series α-trifluoromethyl-β-sulfonyl tertiary alcohols. This new synthetic protocol enabled by charge-transfer complex between oxygen and featuring broad substrate scope scalability. Excellent functional group compatibility chemoselectivity render this method suitable for pharmaceutically relevant molecules. In the presence D2O, deuteriotrifluorinated products were also...

Abstract An unprecedented photoredox‐catalyzed phosphine‐mediated deoxygenation of hexafluoroacetone hydrate was established to accomplish the hydroxylpolyfluoroalkylation electron‐deficient alkenes. A range bis(trifluoromethyl)carbinols were facilely accessed by using readily available hydrate, instead toxic gaseous hexafluoroacetone. alkenes are tolerated, giving corresponding hydro‐hydroxylpolyfluoroalkylated products in moderate high yields. Remarkable features this synthetic strategy...

A novel visible-light-driven organocatalytic protocol to access aerobic oxidative cleavage of olefins, promoted by sodium benzene sulfinate, is described herein. An array alkenes smoothly delivered the corresponding aldehydes and ketones under transition-metal-free conditions. Notably, α-halo-substituted styrenes proceeded with photoinduced oxidation finally afford α-halo-acetophenones halogen migration. Crucial this was formation charge-transfer complexes between sulfinate molecular O2...

Reported herein is a photoredox-catalyzed amination of o-hydroxyarylenaminones with tert-butyl ((perfluoropyridin-4-yl)oxy)carbamate, versatile amidyl-radical precursor developed in our laboratory. This work establishes new cascade pathway for the assembly range 3-aminochromones under mild conditions. Downstream transformations obtained to construct diverse amino pyrimidines greatly broaden applications this photocatalyzed protocol.

Herein, a dual photoredox/nickel catalyzed formylation of aryl bromide with commercially available 2,2-dimethoxy-N,N-dimethylethan-1-amine as an effective CO source has been successfully achieved, delivering series aromatic aldehydes in moderate to good yields. Compared the traditional reductive carbonylation process, this newly designed synthetic protocol provides straightforward toolbox access aldehydes, obviating use carbon monoxide and stoichiometric reductants. Finally, utility direct...

A metal-free photosensitized 1,2-imino-sulfamoylation of olefins by employing a tailor-made sulfamoyl carbamate as the difunctionalization reagent has been established. This protocol exhibits versatility across broad substrate scope, including aryl and aliphatic alkenes, leading to synthesis diverse β-imino sulfonamides in moderate good yields. method is characterized its reaction system, mild conditions, excellent regioselectivity, high atom economy, serving promising platform for...

Nickel/photoredox catalysis has emerged as a powerful platform for exploring nontraditional and challenging cross-couplings. Herein, metallaphotoredox catalytic protocol been developed on the basis of tertiary amine-ligated boryl radical-induced halogen atom transfer process under blue-light irradiation. A wide variety aryl heteroaryl bromides featuring different functional groups pharmaceutical moieties were facilely coupled to rapidly install C(sp3)-enriched aromatic scaffolds. The...

A visible-light-induced, catalyst-free radical cross-coupling cyclization of diselenides or disulfides with N-allylbromodifluoroacetamide has been developed. This developed protocol exhibits good functional group tolerance and affords a variety 4-thio- 4-seleno-substituted 3,3-difluoro-γ-lactams in moderate to yields. Based on control experiments, plausible radical-radical pathway is proposed.

Reported herein is the design and synthesis of new O-perhalopyridin-4-yl hydroxylamines as shelf-stable versatile amidyl-radical precursors. The novel amination reagents can be easily prepared via a single synthetic step from inexpensive commercially available starting materials using monoprotected HONH2 amino source. potency developed was well demonstrated by direct series quinoxalin-2(1H)-ones their analogues under photocatalytic conditions, even without any additive photocatalysts.

Herein, a photoinduced palladium-catalyzed annulation of 1,3-dienes with bifunctional halognated alkylamines has been developed, offering facile route to access broad range vinylpyrrolidines. The reactivity profile this protocol was able be readily manipulated assemble vinylpyrrolidine and vinlysilaazacycle. Remarkably, the utility strategy further illustrated in construction complex biologically important molecules as well diversity-oriented transformations resulting product.

A Giese reaction of aryl bromides with electron-deficient alkenes was developed, enabled by a dual catalyst system containing NiII complex and IrIII photocatalyst. This protocol could accommodate variety alkenes, delivering the conjugate adducts in up to 97% yield. The utilization photoexcited (dtbbpy)NiII(aryl)Br intermediate as an radical source allows this novel transformation halides, thus expanding chemical space excited nickel catalysis.

The oxidative aromatization of aliphatic

Herein, a base-promoted C-P(O) bond formation method has been developed for the phosphorylation of polyfluoroarenes through selective C-F cleavage. The high selectivity and mild, transition-metal-free conditions this underscore its potential sustainable synthesis applications. This expands scope polyfluoroarene functionalization, providing valuable tool incorporating phosphorus motifs in complex aromatic frameworks.