• Issue

    Early View

    Online Version of Record before inclusion in an issue

Concise Reports

Controllable Construction of Vinyl Sulfones and β-Keto Selenosulfones via Selective Oxidative Sulfonylation of Alkenes

  • Version of Record online: 23 February 2024
Description unavailable

The selective electrochemical C—H sulfonylation of alkenes with selenium sulfonate was disclosed. Aerobic trifunctionalization of alkenes occurred by simply changing the conditions, which provides diverse β-keto selenosulfones.

Transition-Metal-Free Allylic Defluorination Cross-Electrophile Coupling Employing Rongalite

  • Version of Record online: 23 February 2024
Description unavailable

A transition-metal-free allylic defluorination reductive cross-coupling between CF3-alkenes and diaryliodonium salts mediated by rongalite has been described for the first time. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates. The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.

Switchable Multicomponent Cyclization Reactions to Access Fluoroalkylated Dihydropyrimidines and Pyrimidines under Solvent-Free Conditions

  • Version of Record online: 23 February 2024
Description unavailable

A switchable strategy for the construction of diverse 4-fluoroalkyl-1,4-dihydropyrimidines and 4-fluoroalkyl-pyrimidines via a solvent/additive-free [3 + 2 + 1] annulation, starting from readily available enamines, trifluoroacetaldehyde hydrate or 1-ethoxy-2,2-difluoroethanol and amidines hydrochloride has been developed.

An Efficient Probe for Bacterial Nitroreductase Imaging and Detection Based on NanoLuc-Furimazine Bioluminescent Pair

  • Version of Record online: 23 February 2024
Description unavailable

A panel of furimazine-based bioluminescent probes has been developed for the detection of pathogenic bacterial nitroreductase. The probe containing 2-nitro-N-methyl-imidazolyl possessed up to a 560-fold increment in bioluminescent intensity, with detection limit as low as 16 ng/mL, making it suitable for bioluminescent visualization in vivo.

Artificial Water Channel Promoting Depolymerization of Actin Filaments to Trigger Cancer Cell Apoptosis

  • Version of Record online: 19 February 2024
Description unavailable

A new strategy to design antitumor reagents has been developed based on artificial water channel (AWC)-promoted depolymerization of actin filaments. Its effectivity has been demonstrated in vitro and in vivo by using colorectal cancer as a disease model. The AWC conjugated with acetazolamide (AZA) moiety exhibited targeting behavior and water permeability to induce the depolymerization of the actin and apoptosis of the cancer cells.

Total Synthesis of Laurane and Guaiane Sesquiterpenoids via Oxidative Nazarov Reaction

  • Version of Record online: 19 February 2024
Description unavailable

We report here the concise total syntheses of four laurane-type and guaiane-type sesquiterpenoids via oxidative Nazarov reaction, using unfunctionalized TDCs as the substrates.

Recent Advances

Hydrogen Bonds in Perovskite for Efficient and Stable Photovoltaic

  • Version of Record online: 13 February 2024
Description unavailable

In this review, we address the important role of hydrogen bonding in improving perovskite solar devices through various additives.

Concise Reports

Asymmetric Synthesis of Dihydrospirotryprostatin B via a Silica Gel-Mediated Cyclization of Tryptamine-Ynamide

  • Version of Record online: 13 February 2024
Description unavailable

An asymmetric synthesis of dihydrospirotryprostatin B was achieved through silica gel-mediated cyclization of tryptamine-ynamide based on a chiral pool strategy.

Comprehensive Reports

Controllable Exciton Diffusion Length and Ultrafast Charge Generation in Ternary Organic Solar Cells

  • Version of Record online: 13 February 2024
Description unavailable

This work demonstrates the feasibility of regulating exciton diffusion and hole transfer to promote efficient charge generation, and achieving high-performance OPV devices by increasing short-circuit current density. Fast and efficient charge generation requires an increased exciton diffusion length and faster hole transfer. In addition, the reduced trap state in the ternary system is also beneficial for reducing recombination of charges. This work reveals the co-mechanism of charge generation and trap state on JSC.

Concise Reports

Chlorajaponins A—Q, Lindenane-Related Sesquiterpenoid Dimers from Chloranthus japonicus and Their Biological Activities

  • Version of Record online: 13 February 2024
Description unavailable

Seventeen new lindenane sesquiterpenoid dimers (LSDs), chlorajaponins A—Q (117), including two rearranged skeleton meroterpenoids (12), and 13 reported analogs (1830) were isolated from the Chloranthus japonicus Sieb. Compounds 1, 2, and 18 demonstrated significant inhibitory effects on lipid accumulation, dose-dependently reduced TG and TC levels, and significantly downregulated expression of FASN and SERBP1 validated by western blot assay. Moreover, compounds 1922 and 25 exhibited the most potent anti-inflammatory effects with IC50 values of 7.89, 6.25, 2.98, 10.77, and 3.60 μmol/L, respectively.

Understanding the Interfacial Energy Structure and Electron Extraction Process in Inverted Organic Solar Cells with Phosphine-Doped Cathode Interlayers

  • Version of Record online: 13 February 2024
Description unavailable

A series of cross-linked and phosphine-doped cathode interlayers (CILs), namely c-NDI:P0, c-NDI:P1, c-NDI:P2, and c-NDI:P3, are developed for inverted organic solar cells. We elucidate the relationship between the depletion region width at the heterojunction interface and the electron extraction ability of CILs. By incorporating c-NDI:P0, a low depletion width of 0.8 nm along with a high power conversion efficiency (PCE) of 17.7% can be obtained in the inverted OSC based on PBDB-TF:BTP-eC9.

Immobilizing Triphenylamine with Photoredox Inert Sr2+ Forming Sr-MOF with Controlled Electron Migration for Photocatalytic Oxidation of Thiols to Disulfides

  • Version of Record online: 12 February 2024
Description unavailable

The immobilization of triphenylamine into MOF with photoredox inert Sr nodes can successfully control the photo-generated electrons transfer from the excited triphenylamine to O2 and realize the heterogeneous catalytic oxidation of thiols to disulfides.

Synthesis of Diverse Oxetane Amino Acids via Visible-Light-Induced Photocatalytic Decarboxylative Giese-Type Reaction

  • Version of Record online: 12 February 2024
Description unavailable

The divergent synthesis of versatile 3,3’-disubstituted oxetane amino acids by utilizing visible-light-induced photocatalytic decarboxylative Giese-type reaction has been demonstrated.

Induced Absolute Configuration of Achiral Tetradentate Ligands in Metal–Organic Frameworks for Circularly Polarized Luminescence

  • Version of Record online: 09 February 2024
Description unavailable

Chiral induction agent can control the formation of the absolute configuration of racemate ligands. Two pairs of homochiral metal-organic frameworks (MOFs) were synthesized with the presence of enantiopure camphoric acid (D/L-cam). Importantly, DCF-17 and LCF-17 exhibit the efficient circularly polarized luminescent (CPL) activity with a luminescence dissymmetry factor (glum) value of –1.0 × 10–2 and +9.2 ×10–3, respectively.

Breaking Reports

C—F Bond Insertion into Indoles with CHBr2F: An Efficient Method to Synthesize Fluorinated Quinolines and Quinolones

  • Version of Record online: 06 February 2024
Description unavailable

A mild and practical method for synthesizing fluorinated quinoline derivatives, which have a wide range of applications in pharmaceuticals, materials, and organic synthesis, was described through C—F bond insertion into indoles using CHBr2F. The simple conditions, readily availability of CHBr2F, as well as the versatility of the transformations make this strategy very powerful in synthesizing 3-fluoroquinoline and 3-fluoroquinolone.

Concise Reports

Reduced Macrophage Uptake of Nanoparticles through Surface Modification of Polypeptides with Valine Residues

  • Version of Record online: 06 February 2024
Description unavailable

The incorporation of valine residues into the polypeptide coatings significantly reduced the macrophage uptake of the nanoparticles, which was not observed for the nanoparticles modified with other amino acid residues like leucine, phenylalanine, isoleucine, and norvaline.

Regularly Tuning Quantum Interference in Single-Molecule Junctions through Systematic Substitution of Side Groups with Varied Electron Effects

  • Version of Record online: 06 February 2024
Description unavailable

Destructive quantum interference of the m-OPE molecules was consistently regulated by substituents with progressively heightened electron effect.

Photoinduced Dehalocyclization to Access Oxindoles Using Formate as a Reductant

  • Version of Record online: 06 February 2024
Description unavailable

A general protocol for the photoinduced dehalocyclization of ortho-halophenylacrylamides with formate has been reported using a CO2 radical anion to access substituted oxindoles.

Critical Reviews

A Comprehensive Review on Mechanisms and Applications of Rare-Earth Based Perovskite Nanocrystals

  • Version of Record online: 05 February 2024
Description unavailable

In lead-based perovskite nanocrystals, a fraction of lead is substituted with rare earth elements for the purpose of doping. Given the adverse effects of lead on human health and the environment, the complete substitution of lead with rare earth ions to achieve lead-free characteristics has emerged as a prominent trend.

Breaking Reports

Encouraging Solution to the Problem of Synthesizing Protein α-Thioester

  • Version of Record online: 05 February 2024
Description unavailable

A facile and robust method to prepare protein α-thioester has been developed. A series of inaccessible protein α-thioesters with limited solubility and internal Cys residues can be efficiently synthesized in one-pot via a SUMO-Protein-Intein sandwich model.

Concise Reports

Twisted Phosphors that Violate Kasha's Exciton Model in Organic Systems

  • Version of Record online: 05 February 2024
Description unavailable

A twisted organic difluoroboron β-diketonate phosphor possessing intramolecular charge transfer character and flexible molecular structure was doped into different organic matrices to fabricate phosphorescence materials. The twisted phosphor adopts different conformation in different matrices. Consequently, the dopant-matrix systems break T1 energy conservation and exhibit distinct phosphorescence wavelengths, violating Kasha's exciton model.

Breaking Reports

Heavier Group 14 Congeners of Metalla-isobenzenes: Access to Metalla-isosilabenzene and Metalla-isogermabenzene by One-Pot Reactions

  • Version of Record online: 05 February 2024
Description unavailable

The derivatives of isosilabenzene and isogermabenzene with metal vinylidene bonds have been achieved from phantom species to stable compounds for the first time. The relative stability of these isomers has been elucidated by experimental observations and DFT calculations.

Concise Reports

Visible-Light-Mediated Photocatalyst-Free Hydroacylation of Azodicarboxylic Acid Derivatives with 4-Acyl-1,4-dihydropyridines

  • Version of Record online: 05 February 2024
Description unavailable

A visible-light-enabled, photocatalyst-free hydroacylation reaction of azodicarboxylic acid derivatives was described, which relied on the dual role of 4-acyl-1,4-dihydropyridine (acyl-DHP) reagents.

Comprehensive Reports

Hole-Transporting Materials with Rational Combination of Pyridine and Dibenzo[a,c]phenazine as Electron Acceptor for Dopant-Free Perovskite Solar Cells

  • Version of Record online: 05 February 2024
Description unavailable

Based on rational combination of dibenzo[a,c]phenazine and pyridine as electronic acceptor and anchoring groups to perovskite layer, DPyP as a hole-transporting material in dopant-free PSC achieved high conversion efficiency of 20.45%, higher than that of DBP (19.77%) based on dibenzo[a,c]phenazine.

Critical Reviews

Nanomedicine Disrupts Stromal Barriers to Augment Drug Penetration for Improved Cancer Therapy

  • Version of Record online: 01 February 2024
Description unavailable

This review summarizes the typical nanostrategies to disrupt tumor stromal barrier for improved cancer therapy, and an up-to-date discussion on some representative studies for deep drug penetration is included, which provides exciting opportunities for designing newly emerging functional biomaterials in this field.

Emerging Topic

Organic Synthesis through Radical Innovation: Frustrated Radical Pairs

  • Version of Record online: 01 February 2024
Description unavailable

Recent developments have led to the emergence of Frustrated Radical Pairs (FRPs) as an extension of the radical family. FRPs are formed from FLPs through Single Electron Transfer (SET) and exhibit the ability to activate a variety of chemical bonds. This review highlights the current state of FRPs in organic synthesis, delves into mechanistic insights, explores their potential, and underscores the challenges in this emerging field.

Recent Advances

Breaking Reports

Access to Versatile Functionalized Cu(III) Complexes Enabled by Direct Transmetalation to Well-Defined Copper(III) Fluoride Complex Me4N+[Cu(CF3)3F]-

  • Version of Record online: 30 January 2024
Description unavailable

The invention of a well-defined Cu(III) fluoride complex Me4N+[Cu(CF3)3(F)]- 1 enabled to access a versatile of functionalized Cu(III) complexes [Me4N]+[Cu(X)(CF3)3]- (X = C6F5, C6F5C≡C, CN, Cl, N3, tBuOO, SCN, OAc, SAr), many of them for the first time. The availability of these complexes allowed us to evaluate the the trans-influence order of ligand in Cu(III) complexes: Bn > CF3 > C6F5 > N3 > py ~ CH3 ~ C6F5C≡C > NO2PhO ~ tBuOO ~ CH3COO > F.

Chemistry Authors Up Close

Homochirality in Ferroelectrochemistry

  • Version of Record online: 30 January 2024
Description unavailable

Introducing homochirality provides an effective and universal strategy to precisely design molecular ferroelectrics. This review summarizes the recent progress on the chemical design of molecular ferroelectrics through the strategy of introducing homochirality.

Recent Advances

Concise Reports

Atroposelective Synthesis of 2-Arylindoles via Chiral Phosphoric Acid-Catalyzed Direct Amination of Indoles

  • Version of Record online: 23 January 2024
Description unavailable

Herein, we developed a general and mild catalytic electrophilic amination of 2-arylindoles with p-quinone diimines to construct axially chiral 2-arylindoles under mild conditions. With the proper choice of a chiral phosphoric acid and substituted 2-arylindoles, the intermolecular C—N bond formation with various p-quinonediimines proceeded with good yields and high stereoselectivities. This strategy provides a powerful method for enantioselective synthesis of 2-arylindole atropisomers which successfully overcame the challenges in catalytic asymmetric construction of axially chiral five-membered heterobiaryls.

Artemsieverolactones A—H, Eight Guaiane-Type Sesquiterpenoid Trimers from Artemisia sieversiana

  • Version of Record online: 23 January 2024
Description unavailable

Bioassay-guided investigation led to the discovery of eight novel guaiane-type sesquiterpenoid trimers, artemsieverolactones A—H, which can be classified into four different types based on the connecting models of three guaianolide units. Most of the compounds showed inhibitory activity on HSC-LX2 cells. Artemsieverolactone B (2) exhibited significant inhibition on HSC-LX2 with an IC50 value of 37.8 μmol/L, and inhibited the deposition of human collagen type I (Col I), human hyaluronicacid (HA) and human laminin (HL) with IC50 values of 40.4, 47.3 and 55.1 μmol/L, respectively.

1,3-Dipolar Cycloaddition of Polycyclic Aromatic Azomethine Ylides and Alkynylbenziodoxoles for Synthesis of Functional Dibenzoullazines

  • Version of Record online: 23 January 2024
Description unavailable

A new family of dibenzoullazine derivatives was synthesized through 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with alkynylbenziodoxoles followed by oxidation. The benziodoxole moiety in the resulting products was used as a versatile linchpin for the synthesis of structurally diverse functional dibenzoullazines that are difficult to access by other synthetic methods.

Direct Analysis of Whole Blood by a Disposable Monolithic Column Mass Spectrometry Analysis Kit

  • Version of Record online: 22 January 2024
Description unavailable

A disposable monolithic column mass spectrometry analysis kit was developed for direct whole blood analysis. The monolithic column can clean whole blood matrix in 30 s as well as avoid analyte exposure to oxygen, moisture and sunlight for sample storage. This MS kit has been successfully applied to the quantitative analysis of procainamide hydrochloride in 2 μL rat blood, proving it a cost-effective and powerful tool for in vitro diagnostics in the future.

Ru(II)-Catalyzed ortho C—H Allylation of N-Aryl-7-azaindoles with 2-Methylidene Cyclic Carbonate

  • Version of Record online: 22 January 2024
Description unavailable

We used Ru(II)-catalyst to perform ortho C—H allylation of N-aryl-7-azaindole with 2-methylenecyclic carbonate. The range of reactions is quite wide, and reactions can also be carried out on other heterocyclic compounds, and different carbonates can be used.

Electrochemical Oxygen Evolution Performance of Nitrogen-Doped Ultra-Thin Carbon Nanosheets Composite Ru1Co Single Atom Alloy Catalysts

  • Version of Record online: 21 January 2024
Description unavailable

A one-step pyrolysis method was employed to load Ru1Co single atom alloy onto a nitrogen-doped ultra-thin carbon sheet, resulting in an electrocatalytic oxygen evolution catalyst suitable for use in an acidic environment. The catalyst exhibited excellent activity and stability in oxygen evolution, with an overpotential of only 238 mV at a current density of 10 mA·cm–2. The structure of the single atom alloy was characterized using synchrotron radiation, which confirmed the involvement of Ru in the oxygen evolution process. Moreover, this approach maximized the utilization efficiency of Ru atomic sites and effectively reduced catalytic costs.

Critical Reviews

Emerging Topic

Exploration of Strong Metal-Support Interaction in Heterogeneous Catalysts by in situ Transmission Electron Microscopy

  • Version of Record online: 18 January 2024
Description unavailable

Strong metal-support interactions (SMSI) are a key concept in heterogeneous catalysis, which govern the catalytic performance in various processes. We here provide a brief summary of the recent progress utilizing in situ TEM to study the SMSI phenomenon and the relationship between structure and performance of the supported catalyst under reaction conditions. Meanwhile, a brief perspective about the use of in situ TEM for further study of SMSI is also presented, showing prospects in this field that will stimulate upsurging research in promoting the catalytic efficiency of supported catalysts.

Concise Reports

Thermoelectric Properties of an Indandione-Terminated Quinoidal Compound: Effect of the n-Type Dopants

  • Version of Record online: 18 January 2024
Description unavailable

Indandione-terminated quinoidal compound Q-4F was doped using two n-dopants N-DMBI and LCV through solution process. N-DMBI exhibited a higher doping ability for Q-4F than LCV. However, unperturbed molecular packing and favorable morphology can be realized after LCV doping, thereby leading to a high thermoelectrics performance.

Tailoring the Properties of Polyhydroxyalkanoates from Plastics to Elastomers via Stereoselective Copolymerizations of rac-β-Butyrolactone and β-Propiolactone

  • Version of Record online: 18 January 2024
Description unavailable

The ring-opening copolymerizations of racemic-β-butyrolactone (rac-β-BL) and β-propiolactone (β-PL) were performed using the syndio-selective amino-alkoxy-bis(phenolate)-yttrium catalyst, resulting in polyhydroxyalkanoates with tunable properties comparable to traditional fossil-based plastics. Moreover, through one-pot synthesis, we transformed the copolymers into soft and ductile thermoplastic elastomers by utilizing monomers' different copolymerization rates and a bifunctional initiator.

Visible-Light-Driven Four-Component Radical Relay Aminocarbonylation of Unactivated Alkenes

  • Version of Record online: 18 January 2024
Description unavailable

A visible-light-driven four-component radical relay aminocarbonylation reaction of unactivated alkenes using 4CzIPN as an organic photocatalyst is developed, providing robust access to β-fluoroalkyl amides with good yields and selectivity under metal-free conditions. Importantly, this strategy also shows good compatibility with tertiary carbon radicals.

Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides in a Continuous-Flow Cell

  • Version of Record online: 18 January 2024
Description unavailable

An electrochemical dearomative spirocyclization of N-acyl sulfonamides in a continuous-flow cell was reported. This reaction is simple and efficient, and 10 g scale-up synthesis can be readily achieved without external catalysts or supporting electrolytes.

Synergistic Brønsted Base/Photoredox-Catalyzed Three-Component Coupling with Malonates to Synthesize δ-Hydroxy Esters and δ-Keto Esters

  • Version of Record online: 18 January 2024
Description unavailable

Herein, we describe a redox-neutral three-component 1,2-dialkylation from malonates, styrenes, and aldehydes through the synergistic Brønsted base/photoredox catalyzed radical-polar crossover process, providing an efficient and clean approach to a broad variety of δ-hydroxy esters. This developed protocol features exceptionally mild and transition-metal-free conditions, broad compatibility of substrate scope and functional groups, and high atomic economy. Importantly, photocatalytic three-component 1,2-alkylacylation towards valuable intermediate δ-keto esters was also achieved through the combination of the RPC process and following two-electron oxidation from the same starting materials.

Fish Skin-Inspired Janus Hydrogel Coating for Drag Reduction

  • Version of Record online: 10 January 2024
Description unavailable

Inspired by the skin of Osteichthyes fishes, a Janus hydrogel coating consisting of slippery and sticky layers is successfully prepared by a two-step UV light irradiation at room temperature. The slippery layer replicates the structure of cycloid scales, while the nature of hydrogel mimics the mucus on fish skin. The Janus hydrogel coating possesses prominent mechanical, anti-fouling and drag reduction properties.

A High-Contrast Autolysosome Probe for Detecting Interaction between Autophagosomes and Autolysosomes in Mitophagy

  • Version of Record online: 10 January 2024
Description unavailable

The bifunctional fluorescent probe Mito-Q can not only effectively detect mitochondrial viscosity changes and mitophagy, but also be successfully applied to observe the fusion of mitochondrial-containing autolysosomes and autophagosomes (FMAA).

A Label-Free Deoxyribozyme Sensor for m6A Demethylase Activity Detection

  • Version of Record online: 10 January 2024
Description unavailable

We report a label-free deoxyribozyme (DNAzyme) biosensor for m6A demethylase activity detection. The nucleic acid probes consist of a methylation-blocked DNAzyme strand and a designed substrate strand. When demethylase is present, the m6A group is specifically demethylated, and the cleavage activity of DNAzyme is restored. This allows the cleavage product encoded with G-quadruplex binding to thioflavin T (ThT) to generate fluorescence output signals.

A Disulfide-Based Poly(ether-b-amide) Copolymer with Rapid Self-healing Ability under Moderate Conditions

  • Version of Record online: 10 January 2024
Description unavailable

A disulfide-based poly(ether-b-amide) copolymer with rapid self-healing capability under moderate conditions was successfully prepared by employing polyamide synthesized from 4,4’-dithiodibutyric acid and isophorondiamine as hard segment and PTMO as soft segment, which showed great potential in the fields of low-temperature packaging, sealing and propellants.

Breaking Reports

Ni-Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine

  • Version of Record online: 10 January 2024
Description unavailable

A Ni(II)-catalyzed asymmetric difunctionalization of alkynes is reported. This method involves intermolecular regioselective arylation of the alkynes and intramolecular desymmetrization of dinitriles, enabling the synthesis of enantioenriched azepine derivatives. The reaction exhibits good tolerance toward various functional groups, resulting in high yields and enantioselectivities.

Comprehensive Reports

Controlling Three-Step and Five-Step Spin Transitions by Polymorphism in an FeIII Spin Crossover Complex

  • Version of Record online: 10 January 2024
Description unavailable

[FeIII(H-5-Br-thsa)(5-Br-thsa)]·H2O, which exists in two polymorphic forms that exhibit SCO, is reported. Polymorph 1 exhibits three-step SCO, while polymorph 2 exhibits five-step SCO, which effectively regulates multi-step SCO behavior. Polymorphs 1 and 2 crystallize in different space groups during the entire spin-transition process, and two-step symmetry breaking was observed (PbcnPnc2 → Pbcn for polymorph 1; P21/nPnP21/n for polymorph 2).

Recent Advances

Concise Reports

Metal-Free Synthesis of 2-Aminobenzothiazoles via I2-Catalyzed Tandem Cyclization Reaction of Amines and Carbon Disulfide

  • Version of Record online: 03 January 2024
Description unavailable

A convenient approach for the construction of 2-aminobenzothiazoles via I2-catalyzed tandem cyclization reaction of amines and carbon disulfide has been developed.

Asymmetric Partial Hydrosilylation of 2,2-Difluoro-1,3-diketones with Chiral Frustrated Lewis Pairs

  • Version of Record online: 03 January 2024
Description unavailable

An asymmetric hydrosilylation of 2,2-difluoro-1,3-diketones was successfully realized by using a frustrated Lewis pair of chiral borane and tricyclohexylphosphine as a catalyst to give a variety of α,α-difluoro-β-hydroxyketones in high yields with up to 99% ee.

Nickel-Catalyzed Regio- and Stereoselective Defluorinative Arylation of gem-Difluorinated Cyclopropanes

  • Version of Record online: 02 January 2024
Description unavailable

A nickel-catalyzed cross-coupling of gem-difluorinated cyclopropanes with boronic acids was reported, providing the corresponding arylated 2-fluoroallylic scaffolds with high regioselectivity and Z-stereoselectivity. Mechanistic studies proposed a Ni(II)-fluoroallyl pathway and clarified the origin of the high linear selectivity.

Practical Synthesis of Valbenazine via 1,3-Dipolar Cycloaddition

  • Version of Record online: 02 January 2024
Description unavailable

Valbenazine (Ingrezza), a potent compound that selectively inhibits VMAT2 through an active metabolite HTBZ, has been approved for the treatment of tardive dyskinesia and very recently for chorea associated with Huntington's disease. In this report, a practical synthesis of HTBZ and valbenazine has been achieved, featuring a highly stereoselective 1,3-dipolar cycloaddition and an enzymatic kinetic resolution. The cascade process toward pyrido[2,1-a]isoquinoline including cycloaddition, cleavage of the N—O bond, and lactamization proved to be operationally feasible. The allure of enzymatic resolution developed in this work provides a rapid access to THIQ-fused piperidine in various bioactive substances.

Controlled Synthesis of Metal-Nanoparticles Decorated Block Copolymer Hybrid Particles via Emulsion Confined Self-assembly and Their Catalytic Applications

  • Version of Record online: 02 January 2024
Description unavailable

Metal NPs decorated block copolymer (BCP) hybrid nanomaterials were facilely fabricated via emulsion confined self-assembly and seed-mediated growth strategy. The obtained hybrid nanoparticles exhibited high catalytic efficiency for the reduction of 4-nitrophenol to 4-aminophenol.

Critical Reviews

Concise Reports

Palladium-Catalyzed [4+2] and [6+2] Dipolar Cycloadditions for the Construction of Benzo[d]isothiazole 1,1-Dioxide Fused 1,3-Oxazinanes and 1,3-Oxazocanes

  • Version of Record online: 02 January 2024
Description unavailable

Palladium-catalyzed dipolar [4+2] and [6+2] cycloaddition reactions of benzo[d]isothiazole 1,1-dioxides (BDs) have been developed for the construction of of BD-fused 1,3-oxazinanes and 1,3-oxazocanes derivatives, respectively.

Critical Reviews

Synthesis of Organofluorine Compounds with Acylsilanes

  • Version of Record online: 02 January 2024
Description unavailable

Organofluorine compounds are central in synthetic chemistry, medicinal chemistry and material chemistry. In this review, we summarize the investigations on the synthesis of organofluorine compounds with acylsilanes. For the non-fluorinated acylsilanes, the in situ generation of difluoroenoxysilanes from the reactions of the acylsilanes with trifluoromethylation reagents is the major pathway, leading to the facile preparation of various α,α-difluoroketones. For the fluoroalkylacylsilanes, apart from the in situ generation of difluoroenoxysilanes through anion Brook rearrangement, radical Brook rearrangement of the photoexcited acylsilanes and the selective control of the reactivities of the biradicals pave the way for the synthesis of a variety of organofluorine compounds. In general, most of these reactions gave racemic products, and the asymmetric synthesis of organofluorine compounds with acylsilanes is still rare, which would be a potential direction of this field.

Recent Advances

Concise Reports

Polyaspers A and B, the First Ergosterol-Polyether Adducts with Unprecedented 6/6/6/5/5/6/6/6/6 Nonacyclic Architecture from Aspergillus sp. TJ507

  • Version of Record online: 27 December 2023
Description unavailable

Polyaspers A (1) and B (2), the first ergosterol-polyether adducts, were isolated from Aspergillus sp. TJ507, possessing an unequalled 6/6/6/5/5/6/6/6/6 nonacyclic system. 3 could suppress the inflammatory response simulated with TNF-α in HaCaT cells, and in an imiquimod-induced psoriasis murine model, 3 significantly restrained the development of psoriasis symptoms and reduced the expression of IL-17 and IL-23, presenting an anti-psoriatic effect.

An Isolable Phosphinogermylyne as a Synthon of One-Coordinate GeI Radical

  • Version of Record online: 20 December 2023
Description unavailable

A phosphinogermylyne was isolated and fully characterized, which could serve as a synthon of a one-coordinate GeI radical.

Enantioselective Synthesis of Benzimidazole Atropisomers Featuring a N-N Axis

  • Version of Record online: 20 December 2023
Description unavailable

The first enantioselective synthesis of N-N benzimidazole atropisomers via Pd-catalyzed enantioselective intramolecular Buchwald-Hartwig amination reaction was reported. A broad range of nonbiaryl benzimidazole and indole-benzimidazole atropisomers were conveniently accessed in high yields and with excellent enantioselectivities.

Asymmetric Two-Component Alkenyl Catellani Reaction for the Construction of C—N Axial Chirality

  • Version of Record online: 20 December 2023
Description unavailable

An asymmetric two-component alkenyl Catellani reaction for the construction of C—N axial chirality is reported. This method is based on a palladium/chiral norbornene cooperative catalysis and an axial-to-axial chirality transfer process.

Supported Atomically Dispersed Pd Catalyzed Direct Alkoxylation and Allylic Alkylation

  • Version of Record online: 20 December 2023
Description unavailable

The direct allylic alkylation of nucleophiles using allylic alcohols was realized by supported atomically dispersed Pd1/TiO2-EG under the mild neutral condition without using any additives. The distinct performance was attributed to the hydrogen bonds-assisted removing of –OH at the organic-inorganic interface.

Effect of Hyperconjugation on Photovoltaic Performance in Pseduo-2D Perylene Diimide Derivatives

  • Version of Record online: 20 December 2023
Description unavailable

This work firstly unravels the effect of intermolecular σ-π hyperconjugation on the molecular packing and further the optoelectronic properties.

Synthesis of Planar-Chiral [2.2]Paracyclophane-Based Oxazole-Pyrimidine Ligands and Application in Nickel-Catalyzed 1,2-Reduction of α,β-Unsaturated Ketones

  • Version of Record online: 20 December 2023
Description unavailable

The [2.2]paracyclophane-derived oxazole-pyrimidine ligands with planar chirality (PYMCOX) were designed, synthesized and successfully applied in nickel-catalyzed asymmetric 1,2-reduction of α,β-unsaturated ketones, affording the chiral allyilic alcohols with up to 99% yield and 99% ee. Meanwhile, this reduction reaction could be conducted on gram scale without loss of activity and enantioseletivity, and the chiral ligand could be conveniently recovered with high yield.

Comprehensive Reports

Semicrystalline Unfused Polymer Donors with Backbone Halogenation toward Cost-Effective Organic Solar Cells

  • Version of Record online: 20 December 2023
Description unavailable

A novel class of low-cost unfused polymer donors was developed with the regulated backbone planarity by halogenation, which facilitates the molecular self-assembly for favorable film morphology. Our results provide insight into the effects of backbone halogenation on the optoelectronic properties of fully unfused polymer donors and demonstrate a simple backbone motif for the further commercialization of cost-effective OSCs.