Radical Alkylcyanation of 1,6-Enynes with Isonitriles as Bifunctional Reagents.

We report a radical cyano-cyclization of 1,6-enynes with isonitriles via photochemically driven nickel catalysis, forging alkenyl nitrile-tethered γ-lactams under mild conditions. This reaction leverages the photoexcitation of generated nickel (isonitrile) species to facilitate isonitriles serving as alkyl radical precursors and cyanide sources. The reaction accommodates a wide range of substrates, exhibiting excellent regioselectivity and / stereoselectivity.

Defluorinative Alkylboration of Alkenes Enabled by Dual Photoredox and Copper Catalysis.

A regioselectivity reversed three-component defluorinative alkylboration of alkenes with trifluoromethyls and bis(pinacolato)diboron via dual photoredox/copper catalysis is reported. The mild conditions are compatible with a wide array of nonactivated trifluoromethyl aromatics bearing electron-donating or electron-neutral substituents, trifluoroacetamides, and various nonactivated terminal and internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl boronates with high efficiency. Furthermore, this protocol is applicable to alkene-tethered trifluoromethyl aromatics to furnish gem-difluoromethylene-containing cyclic compounds.

Divergent 1,2-carboallylation of terminal alkynes enabled by metallaphotoredox catalysis with switchable triplet energy transfer.

We report a metallaphotoredox strategy for stereodivergent three-component carboallylation of terminal alkynes with allylic carbonates and alkyl trifluoroborates. This redox-neutral dual catalytic protocol utilizes commercially available organic photocatalyst 4CzIPN and nickel catalysts to trigger a radical addition/alkenyl-allyl coupling sequence, enabling straightforward access to functionalized 1,4-dienes in a highly chemo-, regio-selective, and stereodivergent fashion. This reaction features a broad substrate generality and a tunable triplet energy transfer control with pyrene as a simple triplet energy modulator, offering a facile synthesis of complex - and -selective skipped dienes with the same set of readily available substrates.

High-Rate Lithium-Selenium Batteries Boosted by a Multifunctional Janus Separator Over a Wide Temperature Range of -30 °C to 60 °C.

Lithium-selenium batteries are characterized by high volumetric capacity comparable to Li-S batteries, while ≈10 times higher electrical conductivity of Se than S is favorable for high-rate capability. However, they also suffer from the "shuttling effect" of lithium polyselenides (LPSes) and Li dendrite growth. Herein, a multifunctional Janus separator is designed by coating hierarchical nitrogen-doped carbon nanocages (hNCNC) and AlN nanowires on two sides of commercial polypropylene (PP) separator to overcome these hindrances.

Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes.

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development of a catalytic, easily tunable synthetic approach for the stereodivergent synthesis of both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report a photoredox and nickel dual catalytic strategy for the stereodivergent sulfonylalkenylation of terminal alkynes with vinyl triflates and sodium sulfinates under mild conditions.

Light-Induced Divergent Cyanation of Alkynes Enabled by Phosphorus Radicals.

A photochemically induced selective and divergent cyanation reaction of alkynes, enabled by phosphorus radicals, is described. With the use of simple triarylphosphine as a co-catalyst, three cyanation reactions, including di-hydrocyanation, anti-Markovnikov hydrocyanation, and domino hydrocyanation/reduction, can be divergently achieved, furnishing a wide array of alkyl dinitriles, alkenyl nitriles, and alkyl nitriles under mild conditions. Terminal and internal alkynes are applicable with high efficiency and excellent selectivity.

Anion Exchange Affinity-Based Controllable Surface Imprinting Synthesis of Ultrathin Imprinted Films for Protein Recognition.

Anion exchange affinity-based controllable surface imprinting is an effective approach to overcome low imprinting efficiency and high non-specific binding capacity. The template proteins were first immobilized on the anchored tetraalkylammonium groups of the nanoparticles via anion exchange affinity-based interactions, enabling monolayer sorption using a low template concentration. The combined use of surface-initiated photoiniferter-mediated polymerization to precisely control the imprinted film thickness, allowing the formation of homogeneous binding cavities, and the construction of effective binding sites resulted in a low non-specific binding capacity and high imprinting efficiency.

Electromagnetic forces in nanoparticles made of multilayer hyperbolic metamaterials.

We theoretically study the electromagnetic forces (optical gradient force, optical torque and vacuum friction) acting on a spherical anisotropic nanoparticle, which can be characterized by multilayer hyperbolic metamaterials (mHMMs). We find three important results about these forces: (i) Firstly, we theoretically demonstrate that the optical gradient force produced on a mHMMs nanoparticle can be flexibly tuned, from pushing the particle to pulling it, just via changing incident angle of illuminating plane light wave. (ii) Secondly, we find the optical torque acting on the mHMMs nanoparticle (its filling factor is around 0.

Catalyst-Free Intermolecular Sulfonyl/Fluoromethyl Heteroarylation of Vinyl Ethers via Visible-Light-Induced Charge Transfer.

We report a visible-light-induced three-component sulfonyl-heteroarylation of vinyl ethers with sulfinates and five-membered heteroaryl chlorides. This protocol proceeds via electron-donor-acceptor (EDA) complexes between sulfinates and heteroaryl chlorides, giving β-sulfonyl alkyl five-membered heteroarenes with high efficiency and excellent regioselectivity under mild and catalyst-free conditions. Utilization of CF SO Na or CF HSO Na as coupling partners further achieves three-component fluoromethyl-arylation of vinyl ethers, furnishing a series of valuable CF /CF H-incorporated alkyl heterocycles under mild conditions.

Selective Fluoromethyl Couplings of Alkynes via Nickel Catalysis.

We describe here a Ni-catalyzed intermolecular carbo-fluoromethylation of alkynes with aliphatic halides and fluoromethyl halides (BrCF H and ICH F) in the presence of zinc, enabling the facile and selective access to a diverse range of biologically valuable CF H/CH F-incorporated alkenes with excellent regio- and stereoselectivity. Notably, merging intramolecular radical cyclization with fluoromethyl coupling enables the expedient constructions of CF H/CH F-incorporated lactones and lactams with high efficiency and selectivity. Mechanistic studies disclose that this catalytic protocol proceeds via a radical addition to an alkyne followed by selective coupling with the fluoromethyl unit.

Divergent Aminocarbonylations of Alkynes Enabled by Photoredox/Nickel Dual Catalysis.

A metallaphotoredox-catalyzed strategy for the selective and divergent aminocarbonylation of alkynes with amines and 1 atm of CO is reported. This synergistic protocol not only enables the Markovnikov-selective hydroaminocarbonylation of alkynes to afford α,β-unsaturated amides, but also facilitates a sequential four-component hydroaminocarbonylation/radical alkylation in the presence of tertiary and secondary alkyl boronate esters, which allows for straightforward conversion of alkynes into corresponding amides. Preliminary mechanistic studies disclose that a photoinduced oxidative insertion of aniline and CO into nickel followed by a migratory insertion of (carbamoyl)nickel species could be involved.

Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel.

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction of complex motifs. Despite remarkable progress, novel and efficient methods for achieving such transformations under milder conditions with chemo-, regio-, and stereoselectivity still remain a significant challenge; thus, their development is highly desirable. Recently, the merging of nickel catalysis with radical chemistry offers a new and benign platform for the catalytic dicarbofunctionalization of unsaturated π bonds with unprecedented reactivity and selectivity.

Reductive hydrobenzylation of terminal alkynes photoredox and nickel dual catalysis.

A photoredox/nickel dual catalyzed reductive hydrobenzylation of alkynes and benzyl chlorides by employing alkyl amines as a stoichiometric reductant is described. This synergistic protocol proceeds Markovnikov-selective migratory insertion of an alkyne into nickel hydride, followed by cross-coupling with benzyl chloride, providing facile access to important 1,1-disubstituted olefins. This reaction enables the generation of nickel hydride by utilizing readily available alkyl amines as the hydrogen source.

Organic-photoredox-catalyzed three-component sulfonylative pyridylation of styrenes.

An efficient, metal-free protocol for the three-component sulfonylative pyridylation of styrenes organic-photoredox catalysis is described. This metal-free process enables the direct and selective installation of sulfonyl and heteroaryl motifs and tolerates a wide array of functional groups as well as complex molecular scaffolds, that could complement previous methods and would be of interest in pharmaceutical research.

General Method for Enantioselective Three-Component Carboarylation of Alkenes Enabled by Visible-Light Dual Photoredox/Nickel Catalysis.

A visible-light-promoted photoredox/nickel protocol for the enantioselective three-component carboarylation of alkenes with tertiary and secondary alkyltrifluoroborates and aryl bromides is described. This redox-neutral protocol allows for facile and divergent access to a wide array of enantioenriched β-alkyl-α-arylated carbonyls, phosphonates, and sulfones in high yields and excellent enantioselectivities from readily available starting materials. We also report a modular and enantioselective synthesis of flurbiprofen analogs and piragliatin lead compound to demonstrate synthetic utility.

Silver-Enabled General Radical Difluoromethylation Reaction with TMSCF H.

A silver-mediated oxidative difluoromethylation of styrenes and vinyl trifluoroborates with TMSCF H is reported for the first time. This method enables direct and facile access to CF H-alkenes from abundant alkenes with excellent functional-group compatibility. Moreover, this Ag/TMSCF H protocol could further enable a series of radical difluoromethylation reactions of a wide array of substrates, offering a generic and complementary platform for the construction of diversified C-CF H bonds.

Identifying critical outbreak time window of controversial events based on sentiment analysis.

The response of netizens toward controversial events plays an important guiding role in the development of events. Based on the identification of such responses, this study aimed to determine the critical outbreak time window of events. The microblog texts related to an event were divided into seven emotional categories via multi-emotional analysis to capture the subtle emotions of netizens toward an event, i.

Sequential C-O decarboxylative vinylation/C-H arylation of cyclic oxalates a nickel-catalyzed multicomponent radical cascade.

A selective, sequential C-O decarboxylative vinylation/C-H arylation of cyclic alcohol derivatives enabled by visible-light photoredox/nickel dual catalysis is described. This protocol utilizes a multicomponent radical cascade process, decarboxylative vinylation/1,5-HAT/aryl cross-coupling, to achieve efficient, site-selective dual-functionalization of saturated cyclic hydrocarbons in one single operation. This synergistic protocol provides straightforward access to sp-enriched scaffolds and an alternative retrosynthetic disconnection to diversely functionalized saturated ring systems from the simple starting materials.

Selective, Intermolecular Alkylarylation of Alkenes via Photoredox/Nickel Dual Catalysis.

A regioselective, intermolecular 1,2-alkylarylation of alkenes with aryl halides and alkyl oxalates has been developed via photoredox/nickel dual catalysis. This dual-catalytic protocol involves a radical relay process, where radical addition is followed by a nickel-assisted coupling, forging two consecutive C-C bonds in a single operation. The mild and redox-neutral conditions allow for good compatibility in the scope of olefins, (hetero)aryl halides, as well as alkyl oxalates.

Enhancement in Power Conversion Efficiency of GaAs Solar Cells by Utilizing Gold Nanostar Film for Light-Trapping.

Light trapping, caused by the introduction of metallic nanoparticles, has been demonstrated to enhance photo-absorption in GaAs solar cells. In this study, we successfully synthesized gold nanostar thin film with hot spots and obtained a notable improvement of power conversion efficiency (PCE) in single-junction and three-junction high-performance GaAs solar cells by incorporating the poly (3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layer, which enables a much stronger light trapping capability and scattering enhancement than conventional metal nanostructures. Increases of 5.

Photoredox-catalyzed branch-selective pyridylation of alkenes for the expedient synthesis of Triprolidine.

Alkenylpyridines are important pharmaceutical cores as well as versatile building blocks in organic synthesis. Heck reaction represents one of the most powerful platform for the construction of aryl-substituted alkenes, nevertheless, examples for Heck type coupling of alkenes with pyridines, particularly with branched selectivity, remain elusive. Here we report a catalytic, branch-selective pyridylation of alkenes via a sulfinate assisted photoredox catalysis.

Intermolecular, redox-neutral azidoarylation of alkenes via photoredox catalysis.

An intermolecular, redox-neutral azidoarylation of alkenes with pyridines and TMSN3 has been reported via visible light-induced photoredox catalysis. This protocol utilized a radical addition/radical coupling sequence, allowing for facile and regioselective installation of versatile β-azido pyridines under redox-neutral and mild conditions.

Metal-free, intermolecular carbopyridylation of alkenes visible-light-induced reductive radical coupling.

An efficient, metal-free strategy for the intermolecular three-component carbopyridylation of styrenes, enabled by Hantzsch ester and visible light, has been described. This versatile protocol gives access to important β-CF pyridines, through the regioselective, sequential formation of two C-C bonds without the use of exogenous catalysts. The value of this benign protocol has been demonstrated through functionalizations of natural-product- and drug-based complex molecules.

syn-Selective alkylarylation of terminal alkynes via the combination of photoredox and nickel catalysis.

Substituted alkenes are pivotal structural motifs found in pharmaceuticals and agrochemicals. Although numerous methods have been developed to construct substituted alkenes, a generally efficient, mild, catalytic platform for the conversion of alkynes to this highly functionalized scaffold via successive C-C bond forming steps remains in high demand. Here we describe an intermolecular, regio- and syn-stereoselective alkylarylation of terminal alkynes with tertiary alkyl oxalates via photoredox-Ni dual catalysis.