Featured
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Article
| Open AccessMetal free cross-dehydrogenative N-N coupling of primary amides with Lewis basic amines
While the homo N-N coupling of two NH moieties to form the hydrazide N-N bond is well developed, the crossdehydrogenative hetero N-N coupling remains unevolved. Here the authors present an efficient, PhI(OAc)2-mediated intermolecular N-N cross-coupling of primary benzamides with primary and secondary amines.
- Subban Kathiravan
- , Prakriti Dhillon
- & Ian A. Nicholls
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Article
| Open AccessKeto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water
Hydrogen peroxide photosynthesis is an important reaction that suffers from poor activity due to the high energy barrier of hydrogen extraction in water. Here, we report a keto-form anthraquinone framework that shows promising performance in alkaline conditions.
- Xiangcheng Zhang
- , Silian Cheng
- & Lizhi Zhang
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Article
| Open AccessSolar-driven sugar production directly from CO2 via a customizable electrocatalytic–biocatalytic flow system
Solar-driven artificial food synthesis from CO2 provides an approach to overcome the limitations of natural photosynthesis, but it is very challenging. Here, the authors report a hybrid electrocatalytic-biocatalytic flow system, coupling photovoltaics-powered electrocatalysis (CO2 to formate) with a five enzyme cascade platform (formate to sugar), which achieves conversion of CO2 to C6 sugar (L-sorbose) with a solar-to-food energy conversion efficiency of 3.5%.
- Guangyu Liu
- , Yuan Zhong
- & Yujie Xiong
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Article
| Open AccessWater-participated mild oxidation of ethane to acetaldehyde
The direct conversion of low alkane-like ethane into high-value chemicals has posed a significant challenge. Herein, the authors successfully accomplish a one-step conversion of ethane to C2 oxygenates using a Rh single-atom catalyst under mild conditions.
- Bin Li
- , Jiali Mu
- & Yunjie Ding
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Article
| Open AccessSpectroscopic visualization of reversible hydrogen spillover between palladium and metal–organic frameworks toward catalytic semihydrogenation
The authors report an in situ investigation of interfacial hydrogen spillover in Pd/ZIF-8 structures with X-ray and Raman techniques. A mechanistic picture of how Pd/ZIF-8 catalyst mediate alkyne semihydrogenation to alkynes is described.
- Qiaoxi Liu
- , Wenjie Xu
- & Yujie Xiong
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Article
| Open AccessSingle-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis
In addition to maximizing atomic utilization, single-atom catalysts with defined structures can be used to investigate catalytic mechanisms and structure-activity relationships. Here, authors study a non-thermodynamically stable Pt-N2 active site for the electrochemical hydrogen evolution reaction.
- Ziqi Zhang
- , Zhe Zhang
- & Shouhua Feng
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Article
| Open AccessAsymmetric synthesis of P-stereogenic phosphindane oxides via kinetic resolution and their biological activity
P-stereogenic heterocycles are privileged chiral ligands and bioactive compounds, but the catalytic asymmetric synthesis of P-stereogenic phosphindane derivatives is challenging. Here, the authors report a catalytic kinetic resolution of phosphindole oxides via rhodium-catalyzed diastereo- and enantioselective conjugate addition to access enantiopure Pstereogenic phosphindane and phosphindole derivatives.
- Long Yin
- , Jiajia Li
- & Dong Guo
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Review Article
| Open AccessLight-driven polymer recycling to monomers and small molecules
Chemical recycling of plastic enables renewed production of pristine materials, but generally comes at a high energy cost. This review focuses on light-driven approaches for chemically recycling and upcycling plastic waste, with emphasis on reduced energy consumption and selective transformations of challenging to recycle backbone structures.
- Laura Wimberger
- , Gervase Ng
- & Cyrille Boyer
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Article
| Open AccessA restricted dynamic surface self-reconstruction toward high-performance of direct seawater oxidation
Chlorine evolution reaction and deep reconstruction of catalyst are critical issues in direct seawater electrolysis. Here, the authors propose a MoO3/CoO/carbon composite material for improved selective seawater oxidation and restricted dynamic surface self-reconstruction.
- Ling Zhou
- , Daying Guo
- & Shun Wang
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Article
| Open AccessLocking the lattice oxygen in RuO2 to stabilize highly active Ru sites in acidic water oxidation
RuO2 is highly active toward the acidic electrochemical oxygen evolution reaction but exhibits instability due to lattice oxygen oxidation. Here, authors prepare an interstitial Si-decorated RuO2 catalyst with improved stability for acidic water oxidation by suppressing lattice oxygen oxidation.
- Xinyu Ping
- , Yongduo Liu
- & Zidong Wei
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Article
| Open AccessPhoto-induced intramolecular dearomative [5 + 4] cycloaddition of arenes for the construction of highly strained medium-sized-rings
Medium-sized-ring compounds are challenging synthetic targets in organic chemistry. Here the authors report an intramolecular dearomative [5 + 4] cycloaddition of naphthalene-derived vinylcyclopropanes to construct these molecules under visible-light irradiation and a proper triplet photosensitizer.
- Min Zhu
- , Yuan-Jun Gao
- & Shu-Li You
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Article
| Open AccessPulse potential mediated selectivity for the electrocatalytic oxidation of glycerol to glyceric acid
Mitigating the deactivation of noble metal-based catalysts caused by self-oxidation and toxic adsorption poses a considerable challenge in organic electro-oxidation. This study addresses the issue by employing a pulsed potential electrolysis approach to selectively electrocatalyze the oxidation of glycerol to glyceric acid using a Pt-based catalyst.
- Wei Chen
- , Liang Zhang
- & Yuqin Zou
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Article
| Open AccessN-Heterocyclic carbene-catalyzed enantioselective synthesis of planar-chiral cyclophanes via dynamic kinetic resolution
Planar-chiral cyclophanes are important for drug discovery but the enantioselective synthesis of planar-chiral cyclophanes remains challenging. Here the authors describe an N-heterocyclic carbene-catalyzed asymmetric construction of planar-chiral cyclophanes.
- Jiayan Li
- , Ziyang Dong
- & Changgui Zhao
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Article
| Open AccessBubble-water/catalyst triphase interface microenvironment accelerates photocatalytic OER via optimizing semi-hydrophobic OH radical
Temperature has demonstrated the potential to regulate the photocatalytic oxygen evolution reaction (OER). This study confirms that the temperature-induced bubble-water/catalyst triphase interface microenvironment significantly enhances OER by optimizing the formation and deprotonation of semi-hydrophobic OH radicals.
- Guanhua Ren
- , Min Zhou
- & Haifeng Wang
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Article
| Open AccessTailoring d-band center of high-valent metal-oxo species for pollutant removal via complete polymerization
Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) allows for sustainable contamination abatement and resource recovery. Here, authors achieved pollutant removal via complete polymerization by tailoring d-band center of high-valent metal-oxo species.
- Hong-Zhi Liu
- , Xiao-Xuan Shu
- & Han-Qing Yu
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Article
| Open AccessSingle-atom Mo-tailored high-entropy-alloy ultrathin nanosheets with intrinsic tensile strain enhance electrocatalysis
Atomically precise modification of high-entropy alloys is highly appealing for electrocatalysis. Here, the authors design single-atom Mo-tailored high-entropy alloy nanosheets with dilute Pt-Pt ensembles and intrinsic tensile strain for promoting methanol electro-oxidation towards formate.
- Lin He
- , Menggang Li
- & Shaojun Guo
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Article
| Open AccessCobalt catalyzed practical hydroboration of terminal alkynes with time-dependent stereoselectivity
Stereodefined vinylboron compounds are important organic synthons, but the selective generation of the thermodynamically unfavorable Z-isomers remains challenging. Here, the authors develop a cobalt catalytic system, enabling the transformation of terminal alkynes with excellent Z-selectivity, even in the presence of bulky substituents.
- Jinglan Wen
- , Yahao Huang
- & Peng Hu
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Article
| Open AccessLiquid metals for boosting stability of zeolite catalysts in the conversion of methanol to hydrocarbons
For the methanol-to-hydrocarbons process, coke build can rapidly deactivate the zeolite catalyst. Here the authors show that the addition of liquid metal gallium can reduce coke deposition and increase catalyst lifetime.
- Yong Zhou
- , Sara Santos
- & Vitaly V. Ordomsky
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Article
| Open AccessSpatial engineering of single-atom Fe adjacent to Cu-assisted nanozymes for biomimetic O2 activation
Integrating heterogeneous single atom nanozyme (SAzyme) configurations and homogeneous enzyme-like mechanism is promising for optimizing SAzymes but elusive. Here the authors address this issue by developing a spatial engineering strategy to fabricate dual-sites SAzymes incorporating single atom Fe active centers (Fe–N4) and Cu atomic sites (Cu–N4) in a vertically stacked Fe–N4 and Cu–N4 geometry.
- Ying Wang
- , Vinod K. Paidi
- & Kwok-Yin Wong
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Article
| Open AccessEnantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution
Site- and stereoselective C–H functionalization is challenging in the synthetic chemistry, and the catalytic enantioselective C(sp3)–H functionalization based on vinyl cations has scarcely explored. Here, the authors report an asymmetric copper-catalyzed tandem diyne cyclization/unactivated C(sp3)–H insertion reaction via a kinetic resolution.
- Yang-Bo Chen
- , Li-Gao Liu
- & Long-Wu Ye
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Article
| Open AccessSelective hydrodeoxygenation of α, β-unsaturated carbonyl compounds to alkenes
The selective reduction of α, β-unsaturated carbonyls remains a challenge. Here the authors report a zinc-based catalyst for this reaction, converting α, β-unsaturated carbonyl compounds into unsaturated alcohols followed by hydrodeoxygenation to form alkenes.
- Tianjiao Wang
- , Yu Xin
- & Buxing Han
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Article
| Open AccessA Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol
Carbon dioxide hydrogenation is an important industrial reaction. Here, the authors design a CeCuZn catalyst through a metal organic framework template for CO2 hydrogenation to methanol with excellent methanol yield and stability.
- Runping Ye
- , Lixuan Ma
- & Jian Liu
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Article
| Open AccessSurface hydrophobization of zeolite enables mass transfer matching in gas-liquid-solid three-phase hydrogenation under ambient pressure
A modified zeolite nanoreactor with organosilanes boosts hydrogenation of aldehydes/ketones in water at ambient pressure. This method, promoting H2 and substrate mass transfer, achieves a 4.3-fold increase in reaction rate, offering a sustainable approach for organic synthesis under mild conditions.
- Shuai Wang
- , Riming Hu
- & Guozhu Chen
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Article
| Open AccessInterrogating site dependent kinetics over SiO2-supported Pt nanoparticles
Kim and co-workers introduce a new ‘kinetic site deconvolution’ method to identify active sites on heterogeneous catalysts by linking reaction rates to specific adsorption environments.
- Taek-Seung Kim
- , Christopher R. O’Connor
- & Christian Reece
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Article
| Open AccessDesymmetric homologating annulation to access chiral pentafulvenes and their application in bioimaging
Polycyclic/multisubstituted pentafulvenes are of interest as they frequently occur in biologically relevant motifs, electrochromic dyes, and solar cells. Here, the authors report an enantioselective homologating annulation of cyclopent-4-ene-dione with 3-cyano-4-methylcoumarins through L-tert-leucine derived thiourea catalysis, affording a wide range of enantioenriched polycyclic multi-substituted embedded aminopentafulvenes.
- Sanjay Singh
- , Ravi Saini
- & Ravi P. Singh
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Article
| Open AccessCopper nanoparticles encapsulated in zeolitic imidazolate framework-8 as a stable and selective CO2 hydrogenation catalyst
Here, authors report an inter-site structural heterogeneity induced effect of hierarchical single atom Fe catalysts for robust oxygen reduction. Dynamic evolutions and insights into structure-activity relationship are presented.
- Vijay K. Velisoju
- , Jose L. Cerrillo
- & Pedro Castaño
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Article
| Open AccessWood-inspired metamaterial catalyst for robust and high-throughput water purification
Continuous industrialization and human activities have led to severe water quality deterioration. Here, a structure-function integrated system is developed by Douglas fir wood inspired metamaterial catalysts with robust and high throughput water purification performances.
- Lei Zhang
- , Hanwen Liu
- & Jian Lu
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Article
| Open AccessIdentification of a potent palladium-aryldiphosphine catalytic system for high-performance carbonylation of alkenes
The development of stable and efficient ligands is of vital significance to enhance the catalytic performance of carbonylation reactions of alkenes. Here, the authors develop an aryldiphosphine ligand, used in palladium-catalyzed regioselective carbonylation of alkenes, exhibiting high catalytic performance and strong oxygen-resistance stability.
- Kang Zhao
- , Hongli Wang
- & Feng Shi
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Article
| Open AccessA non-canonical nucleophile unlocks a new mechanistic pathway in a designed enzyme
The authors previously showed that a histidine nucleophile and a flexible arginine can work in synergy to accelerate the Morita Baylis-Hillman (MBH) reaction. Here, they report another efficient MBHase that employs a non-canonical Nδ-methylhistidine nucleophile paired with a catalytic glutamate, providing an alternative mechanistic solution for MBH catalysis.
- Amy E. Hutton
- , Jake Foster
- & Anthony P. Green
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Article
| Open AccessSilver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones
Epoxides are prominent small-ring O-heterocycles found in a variety of bioactive natural products and pharmaceuticals. Here, the authors report a silver carbene strategy to achieve O-to-C atom exchange of epoxides in a single step, affording diverse fluoroalkylcyclopropanes.
- Linxuan Li
- , Paramasivam Sivaguru
- & Xihe Bi
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Article
| Open AccessInfluence of electric double layer rigidity on CO adsorption and electroreduction rate
High-pressure infrared spectroscopy shows concentrated cations suppress CO adsorption. Here the authors report two electrochemical interfaces forming distinct double layer structures and reaction rates at elevating pressure and various potentials.
- Jiajie Hou
- , Bingjun Xu
- & Qi Lu
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Article
| Open AccessDioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation
The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.
- Jialiang Wei
- , Junhong Meng
- & Ning Jiao
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Article
| Open AccessCharging modulation of the pyridine nitrogen of covalent organic frameworks for promoting oxygen reduction reaction
The catalytic efficacy of covalent organic frameworks (COFs) is constrained by their restricted electro-transfer capability and weak binding affinities for reaction intermediates. Here the authors report COFs with various pyridinic-based units for tuning their catalytic activity towards oxygen reduction reaction.
- Xiubei Yang
- , Qizheng An
- & Gaofeng Zeng
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Article
| Open AccessSingle-atom tailored atomically-precise nanoclusters for enhanced electrochemical reduction of CO2-to-CO activity
Tailoring catalytic performance of atomically-precise metal nanoclusters catalysts is of great interest but remains challenging. Here, the authors report a co-eletropolymerization strategy to modify well-defined Au8 nanoclusters by single-atom sites to enhance its electrocatalytic activity for the reduction of CO2 towards CO.
- Yi-Man Wang
- , Fang-Qin Yan
- & Shuang-Quan Zang
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Article
| Open AccessZirconium and hafnium catalyzed C–C single bond hydroboration
Selective cleavage and subsequent functionalization of C−C single bonds present a fundamental challenge, and the use of inexpensive and Earth-abundant group IV metals for catalytic C−C single-bond cleavage is largely underdeveloped. Here, the authors report zirconium-catalyzed C−C single-bond cleavage and subsequent hydroboration reactions.
- Sida Li
- , Haijun Jiao
- & Lipeng Wu
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Article
| Open AccessTuning light-driven oxidation of styrene inside water-soluble nanocages
Selective functionalization of C(sp2)–H bonds under ambient conditions is a persistent synthetic challenge in organic chemistry. Here the authors combine host-guest charge-transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration.
- Souvik Ghosal
- , Ankita Das
- & Jyotishman Dasgupta
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Article
| Open AccessContinuous strain tuning of oxygen evolution catalysts with anisotropic thermal expansion
Tuning compressive strain is an effective way to accelerate the oxygen evolution reaction kinetics. Here the authors show that anisotropic thermal expansion induces compressive strains on IrO6 octahedron in Sr2IrO4, shifting its d-band center downward and accelerating water oxidation kinetics beyond traditional thermal diffusion effects.
- Yu Du
- , Fakang Xie
- & Zhigang Zou
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Article
| Open AccessNickel-catalyzed electrophiles-controlled enantioselective reductive arylative cyclization and enantiospecific reductive alkylative cyclization of 1,6-enynes
Transition metal-catalyzed asymmetric cyclization of 1,6-enynes is a powerful tool for the construction of chiral nitrogen-containing heterocycles, but limiting to the use of aryl or alkenyl metal reagents. Here, the authors report Ni-catalyzed enantioselective anti-arylative cyclization and enantiospecific cis-alkylative cyclization of 1,6-enynes.
- Wenfeng Liu
- , Yunxin Xing
- & Kun Shen
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Article
| Open AccessDual-site segmentally synergistic catalysis mechanism: boosting CoFeSx nanocluster for sustainable water oxidation
Efficient oxygen evolution reaction electrocatalysts are essential for sustainable clean energy conversion. Here, the authors propose a Co-Fe dual-site to facilitate the ferromagnetic O-O bond coupling to achieve a great balance between activity and stability.
- Siran Xu
- , Sihua Feng
- & Jia-Nan Zhang
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Article
| Open AccessDistance effect of single atoms on stability of cobalt oxide catalysts for acidic oxygen evolution
Dissolution of Co atoms in acidic media impedes the application of cobalt oxides in proton exchange membrane water electrolyzers. Here, the authors reveal a stabilizing effect induced by Ir single atoms on cobalt oxides that suppress Co dissolution.
- Zhirong Zhang
- , Chuanyi Jia
- & Jie Zeng
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Article
| Open AccessRemote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins
The synthesis of highly substituted olefins has been pursued for decades. Here, the authors show a carbonyl-directed sequential Heck/isomerization/C–H arylation of alkenes for modular synthesis of stereodefined all-carbon tetrasubstituted olefins.
- Runze Luan
- , Ping Lin
- & Weiping Su
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Article
| Open AccessNanocurvature-induced field effects enable control over the activity of single-atom electrocatalysts
Modulating interfacial electric fields provides a means to control electrocatalyst activity for a broad range of reactions. Here the authors show that this can be achieved by tuning the nanocurvature of carbon supported single-atom catalysts.
- Bingqing Wang
- , Meng Wang
- & Yanwei Lum
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Article
| Open AccessCoverage enhancement accelerates acidic CO2 electrolysis at ampere-level current with high energy and carbon efficiencies
The increased surface coverage of CO2 electroreduction (CO2R) intermediates promotes CO2R at high operating current densities under strongly acidic conditions. Here the authors report a 77.4% single-pass carbon efficiency for conversion of acidic CO2R to pure formic acid.
- Xiaohan Yu
- , Yuting Xu
- & Miao Zhong
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Article
| Open AccessIn situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction
The electrochemical oxygen reduction reaction plays an important role in new energy technologies such as fuel cells and metal-air batteries. Here the authors present a cobalt catalyst with a symmetry-broken Cl−Co−N4 moiety capable of dynamically modulating electron occupancy at active sites during practical reaction conditions to optimize oxygen reduction performance.
- Meihuan Liu
- , Jing Zhang
- & Qinghua Liu
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Article
| Open AccessSuperexchange-stabilized long-distance Cu sites in rock-salt-ordered double perovskite oxides for CO2 electromethanation
Cu-oxide-based catalysts are promising for CO2 electromethanation but suffer from inevitable reduction and structural collapse. Here the authors report a Cu-based rock-salt-ordered double perovskite oxide with superexchange-stabilized long-distance Cu sites for efficient and stable CO2 methanation.
- Jiawei Zhu
- , Yu Zhang
- & Heqing Jiang
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Article
| Open AccessCooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline
The oxidative intermolecular amination of C-H bonds represents a straightforward method to construct aliphatic allylic amines. However, the utilization of widely available internal alkenes remains a synthetic challenge. Here, the authors present a regioselective Cu-catalyzed oxidative allylic C-H amination of internal olefins with azodiformates.
- Le Wang
- , Cheng-Long Wang
- & Shu-Yu Zhang
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Article
| Open AccessMetal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes
Enhancing the sp3-hybridized character of molecular structures in drug discovery is paramount. Here, the authors introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation.
- Stefano Bonciolini
- , Antonio Pulcinella
- & Timothy Noël
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Review Article
| Open AccessChallenges and recent advancements in the synthesis of α,α-disubstituted α-amino acids
α,α-Disubstituted α-amino acids (α-AAs) have improved properties compared to other amino acids. Here, the authors provide an overview of the recent advancements since 2015 and discuss existing challenges for their synthesis.
- Yu Zhang
- , Jaro Vanderghinste
- & Shoubhik Das
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Article
| Open AccessIron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay
Stoichiometric amounts of metal reductant and the requirement of a directing group limit the application of transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides. Here, the authors report a reductive difunctionalization of alkenes via a radical-anion relay with Na2S2O4 as both reductant and sulfone-source.
- Xiaoya Hou
- , Hongchi Liu
- & Hanmin Huang