Photoredox-Catalyzed Alkene Acylesterification with Acyloxime Esters via C-C and Tertiary C-O Bond Formation.

We describe an efficient acyl esterification method for alkenes utilizing acyloxime esters as bifunctional reagents featuring radical acylation and congested C-O bond formation. This approach is characterized by mild photoredox conditions, high step and atom economy, a broad substrate scope, and excellent regioselectivity. A variety of valuable α-acyl hindered alcohol esters, including those obtained via gram-scale synthesis and late-stage functionalization of pharmaceutical molecules, were presented, demonstrating its synthetic potential and practicability.

Synthesis of α,α-Difluoromethylene Amines from Thioamides Using Silver Fluoride.

We developed a mild, rapid process employing AgF and thioamides to produce α,α-difluoromethylene amines efficiently. This method exhibited remarkable tolerance toward various functional groups present in -sulfonylthioamides, thereby broadening the scope of difluoromethylene sulfonamides through a straightforward approach. Additionally, we applied this approach to synthesize various perfluoroalkyl amines, establishing practical synthetic routes for exploring these compounds in pharmaceutical chemistry and materials science.

Photoredox-Catalyzed Acylchlorination of α-CF Alkenes with Acyl Chloride and Application as Masked Access to β-CF-enones.

We disclose a photocatalytic strategy that simultaneously addresses the construction of trifluoromethylated quaternary carbon centers and the preparation of β-CF-enones through radical difunctionalization of α-CF alkenes with acyl chlorides. This method is characterized by its broad functional group compatibility, high efficiency, and atom economy. The versatility of this transformation is poised to broaden the applications of α-CF alkenes, providing new pathways for the rapid assembly of structurally diverse fluorinated compounds.

Electrocatalysis-Enabled Stereoselective Synthesis of Monofluoroalkenes via Hydrodefluorination of -Difluoroakenes.

We report a simple and economical method to synthesize monofluoroalkenes via the electrochemical hydrodefluorination of -difluoroalkenes. This reaction proceeds efficiently at room temperature, eliminating the requirement for a costly transition metal catalyst, ligand, and external reducing agent. The monofluoroalkene products can be obtained in medium to good yields and up to 99:1 / selectivity.

Electrocatalysis-Enabled Defluorinative Cross-Coupling of -Difluoroalkenes with Aldehydes and Ketones.

An electrochemical defluorinative cross-coupling of -difluoroalkenes with carbonyl compounds was described, by which highly stereoselective monofluoroalkene allyl alcohols were synthesized. The reaction tolerates a broad range of functional groups and has successfully been applied to synthesize complex molecules. Mechanistic studies indicate that the reaction starts from electron reduction of -difluoroalkenes to generate radical negative ions, which undergo β-fluoride elimination and subsequent reduction to form anions.

Photoredox-Catalyzed -Difluoromethylenation of Aliphatic Alcohols with 1,1-Difluoroalkenes to Access α,α-Difluoromethylene Ethers.

A switchable synthesis of alcohols and ketones bearing a CF-OR scaffold using visible-light promotion is described. The method of PDI catalysis is characterized by its ease of operation, broad substrate scopes, and the ability to switch between desired products without the need for transition metal catalysts. The addition or absence of a base plays a key role in controlling the synthesis of the major desired products.

Directing (110) Oriented Lithium Deposition through High-flux Solid Electrolyte Interphase for Dendrite-free Lithium Metal Batteries.

Controlling lithium (Li) electrocrystallization with preferred orientation is a promising strategy to realize highly reversible Li metal batteries (LMBs) but lack of facile regulation methods. Herein, we report a high-flux solid electrolyte interphase (SEI) strategy to direct (110) preferred Li deposition even on (200)-orientated Li substrate. Bravais rule and Curie-Wulff principle are expanded in Li electrocrystallization process to decouple the relationship between SEI engineering and preferred crystal orientation.

Photoredox Catalysis-Enabled C-H Difluoromethylation of Heteroarenes with Pentacoordinate Phosphorane as the Reagent.

Difluoromethylated heterocyclic compounds have found broad applications in numerous bioactive molecules. Herein, we report photoredox catalysis-induced direct C-H difluoromethylation of heterocycles by using bis(difluoromethyl) pentacoordinate phosphorane (PPh(CFH), ) as the reagent. A variety of heterocycles, such as quinoxalin-2(1)-one, thiophene, indole, and coumarin, are readily tailored with a difluoromethyl group.

Visible-Light Photoredox-Catalyzed Divergent 1,2-Diacylation and Hydroacylation of Alkenes with Carboxylic Acid Anhydride.

A photoredox-catalyzed divergent 1,2-dicarbonylation and hydroacylation of alkenes with acid anhydride is presented. This approach offers a mild and efficient entry to 1,4-dicarbonyl compounds bearing all-carbon quaternary centers, exhibiting a broad substrate scope and high functional group compatibility. Hydrocarbonylaltion of alkenes can also be realized by simply introducing a proton source to the reaction system.

CsPbBr perovskite quantum dots grown within Fe-doped zeolite X with improved stability for sensitive NH detection.

All-inorganic cesium lead halide (CsPbX, X = Cl, Br and I) perovskite quantum dots (QDs) have received enormous research interest because of their exceptional optoelectronic properties, but their low chemical stability under ambient conditions from inevitable defects restricts their practical applications. In an effort to enhance the stability of QDs, in this study, novel functional nanocomposites were fabricated by encapsulating perovskite QDs with zeolite X doped with iron ions. Focusing on the as-obtained nanocomposites labeled with QDs@Fe/X-, doping a reasonable amount of Fe ions can tremendously improve the order of perovskite lattices and reduce the halide vacancies.

Synthesis of α-Difluoromethylene Ethers via Photoredox-Induced Hyperconjugative Ring Opening of -Difluorocyclopropanes.

Fluorinated compounds have found widespread applications in pharmaceuticals, agrochemicals, and materials science. Precise construction of α-difluoromethylene ether (CFO) moiety in organic molecules is of high demand. Herein, a visible light-promoted reaction protocol for the synthesis of α-difluoromethylene ether from -difluorocyclopropane is described.

Knowledge atlas of antibody-drug conjugates on CiteSpace and clinical trial visualization analysis.

Objective: Antibody-drugs conjugates (ADCs) are novel drugs with highly targeted and tumor-killing abilities and developing rapidly. This study aimed to evaluate drug discovery and clinical trials of and explore the hotspots and frontiers from 2012 to 2022 using bibliometric methods.

Methods: Publications on ADCs were retrieved between 2012 and 2022 from Web of Science (WoS) and analyzed with CiteSpace 6.

Homogeneous Gold Redox Chemistry: Organometallics, Catalysis, and Beyond.

Gold redox chemistry holds the promise of unique reactivities and selectivities that are different to other transition metals. Recent studies have utilized strain release, ligand design, and photochemistry to promote the otherwise sluggish oxidative addition to Au(I) complexes. More details on the reductive elimination from Au(III) complexes have also been revealed.

Strategies for remote enantiocontrol in chiral gold(iii) complexes applied to catalytic enantioselective γ,δ-Diels-Alder reactions.

The use of chiral square planar gold(iii) complexes to access enantioenriched products has rarely been applied in asymmetric catalysis. In this context, we report a mechanistic and synthetic investigation into the use of N-heterocyclic (NHC) gold(iii) complexes in γ,δ-Diels-Alder reactions of 2,4-dienals with cyclopentadiene. The optimal catalyst bearing a unique 2-chloro-1-naphthyl substituent allowed efficient synthesis of functionally rich carbocycles in good yields, diastereo- and enantioselectivities.

From C to C : Copper-Catalyzed gem-Bis(trifluoromethyl)olefination of α-Diazo Esters with TMSCF.

A Cu-catalyzed gem-bis(trifluoromethyl)olefination of α-diazo esters, using TMSCF as the only fluorocarbon source, has been developed and provides an exquisite method to access gem-bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into "CuCF " to generate the α-CF -substituted organocopper species, which then undergoes β-fluoride elimination and two consecutive addition-elimination processes to give the desired products. The key to this efficient one-pot C -to-C synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem-difluoroalkene intermediates.

Visible Light Driven Alkylation of C(sp)-H Bonds Enabled by 1,6-Hydrogen Atom Transfer/Radical Relay Addition.

A visible-light-driven sulfamate esters guided alkylation of unactivated C(sp)-H bonds enabled by a 1,6-HAT/radical addition cascade is described. Not only structurally diverse Michael acceptors but also styrenes are amenable to this alkylation reaction. Notably, the N-H bonds activation radical relay refrained from prefunctionalization and using excess external oxidants.

TMSCF as a Convenient Source of CF =CF for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation.

A new method for the on-site preparation of tetrafluoroethylene (TFE) and a procedure for its efficient use in pentafluoroethylation by fluoride addition were developed by using a simple two-chamber system. The on-site preparation of TFE was accomplished by dimerization of difluorocarbene derived from (trifluoromethyl)trimethylsilane (TMSCF ) under mild conditions. Other fluoroalkylation reactions, such as (aryloxy)tetrafluoroethylation and tetrafluoroethylation processes, were also achieved using a similar approach.

Copper-Mediated Aromatic 1,1-Difluoroethylation with (1,1-Difluoroethyl)trimethylsilane (TMSCF2 CH3 ).

A new method for the formation of 1,1-difluoroethyl copper species ("CuCF2 CH3 ") with 1,1-difluoroethylsilane (TMSCF2 CH3 ) has been developed. The "CuCF2 CH3 " species can be applied to the efficient 1,1-difluoroethylation of diaryliodonium salts under mild conditions, affording (1,1-difluoroethyl)arenes in good to excellent yields. This convenient procedure tolerates a wide range of functional groups and thus serves as a practical synthetic tool for the introduction of CF2 CH3 group(s) into complex molecules.

Copper-mediated aerobic (phenylsulfonyl)difluoromethylation of arylboronic acids with difluoromethyl phenyl sulfone.

A new method for the generation of the "PhSO2CF2Cu" species from readily available difluoromethyl phenyl sulfone (PhSO2CF2H) has been developed. The "PhSO2CF2Cu" reagent can be applied in (phenylsulfonyl)difluoromethylation of arylboronic acids, which affords a convenient approach to introducing the PhSO2CF2 group into aromatics.

gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors.

A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins.

Copper-mediated trifluoromethylation using phenyl trifluoromethyl sulfoxide.

A new method for the generation of trifluoromethylcopper ("CuCF3") species from readily available phenyl trifluoromethyl sulfoxide has been developed. The "CuCF3" reagent can be applied in efficient trifluoromethylations of aryl iodides and activated aryl bromides in the absence of additional ligands. Furthermore, the "CuCF3" species can also undergo oxidative cross-coupling with terminal alkynes and arylboronic acids.

gem-Difluoroolefination of diaryl ketones and enolizable aldehydes with difluoromethyl 2-pyridyl sulfone: new insights into the Julia-Kocienski reaction.

The direct conversion of diaryl ketones and enolizable aliphatic aldehydes into gem-difluoroalkenes has been a long-standing challenge in organofluorine chemistry. Herein, we report efficient strategies to tackle this problem by using difluoromethyl 2-pyridyl sulfone as a general gem-difluoroolefination reagent. The gem-difluoroolefination of diaryl ketones proceeds by acid-promoted Smiles rearrangement of the carbinol intermediate; the gem-difluoroolefination is otherwise difficult to achieve through a conventional Julia-Kocienski olefination protocol under basic conditions due to the retro-aldol type decomposition of the key intermediate.

Copper-mediated trifluoromethylthiolation of α-diazoesters.

A novel Cu-mediated trifluoromethylthiolation of diazo compounds has been developed that provides a convenient synthetic route for the efficient α-trifluoromethylthiolation of simple esters under mild reaction conditions. The reaction is typically carried out at room temperature, and water could be used to promote the reaction.