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Article
| Open AccessA facile synthesis of α,β-unsaturated imines via palladium-catalyzed dehydrogenation
α,β-unsaturated compounds serve as versatile synthons in organic chemistry, but the α,β-desaturation of aliphatic imines is challenging due to easy hydrolysis and preferential dimerization. Herein, the authors report the synthesis of α,β-unsaturated imines by employing a pre-fluorination and palladium-catalyzed dehydrogenation reaction sequence.
- Chunyang Zhao
- , Rongwan Gao
- & Junkai Fu
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Article
| Open AccessPara-selective nitrobenzene amination lead by C(sp2)-H/N-H oxidative cross-coupling through aminyl radical
Direct radical C–H amination strategies have exhibited innovation, but challenges remain with C–H amination of electron-poor nitroarenes due to the essence of the electron-deficient nitrogen radical. Herein, the authors report a transition metal-free dehydrogenative C(sp2)-H/N-H cross-coupling between electron-poor nitroarenes and amines.
- Zhen Zhang
- , Shusheng Yue
- & Hu Cai
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Article
| Open AccessIntroduction of the difluoromethyl group at the meta- or para-position of pyridines through regioselectivity switch
The direct C−H-difluoromethylation of pyridines represents a highly efficient economic way to access azines. However, the direct meta-difluoromethylation of pyridines remains elusive. Here, the authors demonstrate switchable meta- as well as para-C−H difluoromethylation of pyridines through radical processes by using oxazino pyridine intermediates.
- Pengwei Xu
- , Zhe Wang
- & Armido Studer
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Article
| Open AccessCapture of single Ag atoms through high-temperature-induced crystal plane reconstruction
Terminal hydroxyl groups on γ-Al2O3 surfaces serve as anchoring sites for Ag. Based on the surface energy of different crystal planes of γ-Al2O3 at various temperatures, the authors propose a high-temperature-induced crystal plane transformation method to construct terminal hydroxyl anchoring sites.
- Jiaxin Li
- , Kai Li
- & Hong He
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Article
| Open AccessOne pot conversion of phenols and anilines to aldehydes and ketones exploiting α gem boryl carbanions
For the carbonylation reactions to synthesize aldehyde, ester, amide, and other carbonyl derivatives, a transition metal-free and CO- free reaction was challenging but highly demanded. Here, the authors report a transition metal-free and CO- free method for deoxygenetive/denitrogenetive conversion of phenols and anilines to aldehydes and ketones.
- Kanak Kanti Das
- , Debasis Aich
- & Santanu Panda
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Article
| Open AccessEnantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch
Catalytic and enantioselective construction of chiral α,α-dialkyl indoles represents an important yet challenging objective to be developed. Herein the authors describe a cobalt catalyzed enantioselective anti-Markovnikov alkene hydroalkylation via the remote stereocontrol for the synthesis of α,α-dialkyl indoles and other N-heterocycles.
- Jiangtao Ren
- , Zheng Sun
- & Zhihui Shao
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Article
| Open AccessCarbon–nitrogen transmutation in polycyclic arenol skeletons to access N-heteroarenes
Developing skeletal editing tools, especially to realize the single-atom transmutation in a ring system without altering the ring size is challenging. Here, the authors introduce a skeletal editing strategy that enables polycyclic arenols to be readily converted into N-heteroarenes through carbon–nitrogen transmutation.
- Hong Lu
- , Yu Zhang
- & Hao Wei
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Article
| Open AccessDinuclear gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes
The widespread use of organoboronic acids has prompted the development of synthetic methodologies to meet the demands on structural diversity and functional group tolerance. Herein, the authors disclose a divergent radical dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation.
- Cheng-Long Ji
- , Hongliang Chen
- & Jin Xie
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Perspective
| Open AccessEmerging trends in chiral inorganic nanomaterials for enantioselective catalysis
Considerable attention has been directed towards chiral nanocatalysts due to their significant role in facilitating asymmetric organic transformations. Here the authors highlight the recent advancements and notable examples in the field of chiral inorganic nanocatalysts.
- Si Li
- , Xinxin Xu
- & Chuanlai Xu
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Article
| Open AccessEfficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions
The conversion of atmospheric N2 into NH3 under ambient pressure is highly interesting but very challenging. In this study, the authors present a tandem air-NOx and NOx-NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx−reduction, resulting in a high NH3 yield from N2 under ambient pressure conditions.
- Wei Liu
- , Mengyang Xia
- & Guidong Yang
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Article
| Open AccessA comprehensive synthetic library of poly-N-acetyl glucosamines enabled vaccine against lethal challenges of Staphylococcus aureus
Poly-β-(1–6)-N-acetylglucosamine (PNAG) is an important vaccine target, but the impact of the number and position of free amine vs N-acetylation on its antigenicity is not well understood. Here, the authors report a divergent strategy to synthesize a comprehensive library of PNAG pentasaccharides, enabling the identification of enhanced epitopes for vaccines against Staphylococcus aureus including drug resistant strains.
- Zibin Tan
- , Weizhun Yang
- & Xuefei Huang
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Article
| Open AccessAn isolable, chelating bis[cyclic (alkyl)(amino)carbene] stabilizes a strongly bent, dicoordinate Ni(0) complex
Notwithstanding their success as strongly σ-donating and π-accepting ligands, to date no chelating bis[cyclic (alkyl)(amino)carbenes] have been reported. Here the authors describe a chelating, C2-symmetric bis[cyclic (alkyl)(amino)carbene] ligand, as well as its pseudotetrahedral complexes with iron, cobalt, nickel, and zinc dihalides.
- Braulio M. Puerta Lombardi
- , Morgan R. Faas
- & Roland Roesler
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Article
| Open AccessDehydroxylative radical N-glycosylation of heterocycles with 1-hydroxycarbohydrates enabled by copper metallaphotoredox catalysis
N-Glycosylated heterocycles play important roles in biological systems and drug development, but the synthesis heavily relies on ionic N-glycosylation. Herein, the authors report a dehydroxylative radical method for synthesizing N-glycosides by leveraging copper metallaphotoredox catalysis.
- Da-Peng Liu
- , Xiao-Sen Zhang
- & Xiang-Guo Hu
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Article
| Open AccessPalladium-catalyzed asymmetric carbene coupling en route to inherently chiral heptagon-containing polyarenes
Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial but the chirality orginiating from the distorted structure around heptagon-containing polyarenes is largely overlooked. Herein the authors present a highly enantioselective synthesis for fabrication of all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross–coupling of benzyl bromides and N-arylsulfonylhydrazones.
- Huan Zhang
- , Chuan-Jun Lu
- & Ren-Rong Liu
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Article
| Open AccessNoncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation
Exploitation of noncovalent interactions has received much attention for the design of metal catalysts. However, because of the weak nature, CH-π interactions have been less utilized for the control of organic reactions. Here, the authors report that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes.
- Yushu Jin
- , Boobalan Ramadoss
- & Laurean Ilies
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Article
| Open AccessStress-induced ordering evolution of 1D segmented heteronanostructures and their chemical post-transformations
The formation mechanisms for periodic heterostructures are still poorly understood. Here, the authors propose a versatile approach to synthesize one-dimensional segmented heterostructures and reveal a stress-induced ordering mechanism through phase-field simulations.
- Qing-Xia Chen
- , Yu-Yang Lu
- & Shu-Hong Yu
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Article
| Open AccessCarbon dioxide capture and functionalization by bis(N-heterocyclic carbene)-borylene complexes
Bis(N-heterocyclic carbene)-borylene complexes are capable of capturing and functionalizing CO2, but stable single-site-boron-carbon dioxide adducts are rarely reported. Here, the authors report the synthesis of a stable borylene-CO2 complex as well as the functionalization of the captured CO2.
- Jun Fan
- , An-Ping Koh
- & Cheuk-Wai So
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Article
| Open AccessClosed-loop recycling of sulfur-rich polymers with tunable properties spanning thermoplastics, elastomers, and vitrimers
Sulfur-rich polymers are promising candidates for chemical recycling but lack efficient synthetic strategies for achieving diverse structures. Here, the authors report a synthesis strategy for polytrithiocarbonates which is compatible with a wide range of monomers enabling diverse structures via polycondensation of dithiols and dimethyl trithiocarbonate.
- Jin-Zhuo Zhao
- , Tian-Jun Yue
- & Wei-Min Ren
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Article
| Open AccessLaMg6Ga6S16: a chemical stable divalent lanthanide chalcogenide
Synthesising chemically stable divalent lanthanide compounds is still faced by great challenges. Here, by using octahedra coupling tetrahedra single/double chains to construct an octahedral crystal field, authors synthesised a stable crystalline La(II)-chalcogenide, LaMg6Ga6S16.
- Yujie Zhang
- , Jiale Chen
- & Hongwei Yu
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Article
| Open AccessExtending carbon chemistry at high-pressure by synthesis of CaC2 and Ca3C7 with deprotonated polyacene- and para-poly(indenoindene)-like nanoribbons
The authors demonstrate that carbides with infinite chains of fused [C6] and [C5] rings are synthesized at deep planetary pressures and temperatures. Hydrolysis of these carbides may lead to polycyclic aromatic hydrocarbons in the Universe.
- Saiana Khandarkhaeva
- , Timofey Fedotenko
- & Leonid Dubrovinsky
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Article
| Open AccessStereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals
C-oligosaccharides are found in natural products and drug molecules, but their synthesis is challenging. Here, the authors report a strategy for the stereoselective and efficient synthesis of Coligosaccharides via palladium-catalyzed nondirected C1–H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors.
- Ya-Nan Ding
- , Mei-Ze Xu
- & Yong-Min Liang
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Article
| Open AccessNi-catalyzed enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohols and aryl bromides
The direct reductive coupling of alkyl alcohol and aryl halide enables efficient access to valuable compounds, but the asymmetric pattern remains unknown. Here the authors describe the enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohol and aryl bromide in the presence of an NHC activating agent.
- Li-Li Zhang
- , Yu-Zhong Gao
- & Ze-Peng Yang
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Article
| Open AccessEnantioselective total synthesis of (‒)-lucidumone enabled by tandem prins cyclization/cycloetherification sequence
The Ganoderma meroterpenoids are a growing class of natural products with a wide range of biological activities. Here, the authors report the enantioselective total synthesis of the Ganoderma meroterpenoid (‒)-lucidumone, featuring a copper-catalyzed enantioselective silicon-tethered intramolecular Diels-Alder cycloaddition to assemble the bicyclo[2.2.2]octane framework and a domino deprotection/Prins reaction/cycloetherification/oxidation sequence to generate concurrenly the tetrahydrofuran and the fused indanone skeleton.
- Xian-Zhang Liao
- , Ran Wang
- & Guang Li
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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 AccessReduction of Li+ within a borate anion
Chemical reduction of alkali cations to their metals is extremely challenging. Here, the authors synthesized a series of redox-active borate anions stabilized by bipyridine ligands which can reduce lithium ions generating elemental lithium metal and borate radicals.
- Haokun Li
- , Jiachen Yao
- & Zhenpin Lu
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Article
| Open AccessEfficient palladium-catalyzed electrocarboxylation enables late-stage carbon isotope labelling
Carbon isotope labelling of bioactive molecules is essential for accessing the pharmacokinetic and pharmacodynamic properties of new drug entities. Here, the authors propose an electrochemical isotope-labelling protocol which enables the use of near-stoichiometric 14CO2, facilitating late-stage and single-step carbon-14 labelling of pharmaceuticals and representative precursors.
- Gabriel M. F. Batista
- , Ruth Ebenbauer
- & Troels Skrydstrup
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Article
| Open AccessA concise and scalable chemoenzymatic synthesis of prostaglandins
Prostaglandins are of interest to synthetic chemists due to their biological activities. Here, the authors present a concise chemoenzymatic synthesis method for several representative prostaglandins, achieved in 5 to 7 steps, via the common intermediate bromohydrin, a radical equivalent of Corey lactone.
- Yunpeng Yin
- , Jinxin Wang
- & Jian Li
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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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Article
| Open AccessTargeted sampling of natural product space to identify bioactive natural product-like polyketide macrolides
Polyketide macrolides are of interest for drug discovery but their inherent structural and stereochemical complexity hinders the exploration of related regions of chemical space more broadly. Here, the authors designed in silico and synthesized a library of tetrahydrofuran-containing polyketide macrolides, and screened them against a panel of biological assays, identifying biologically active library members.
- Darryl M. Wilson
- , Daniel J. Driedger
- & Robert A. Britton
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Article
| Open AccessSynthesis of meta-carbonyl phenols and anilines
Phenols and anilines are of extreme importance for medicinal chemistry and material science but the selective preparation of meta-substituted phenols and anilines remains challenging. Here the authors report an efficient copper-catalyzed dehydrogenation strategy to exclusively synthesize meta-carbonyl phenols and anilines from carbonyl substituted cyclohexanes.
- Bao-Yin Zhao
- , Qiong Jia
- & Yong-Qiang Wang
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Article
| Open AccessPhenol as proton shuttle and buffer for lithium-mediated ammonia electrosynthesis
The proton shuttle plays a critical role in the proton transfer process during lithium-mediated ammonia synthesis. Here, the authors establish the structure-activity relationship and design principles for effective proton shuttles.
- Xianbiao Fu
- , Aoni Xu
- & Ib Chorkendorff
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Article
| Open AccessValence-isomer selective cycloaddition reaction of cycloheptatrienes-norcaradienes
Combining data science and organic synthesis to achieve the rapid and precise creation of complex molecules while controlling multiple selectivities is an emerging trend, but few successful examples are reported. Here, the authors develop an artificial neural network regression model using bond orbital data to predict chemical reactivities.
- Shingo Harada
- , Hiroki Takenaka
- & Tetsuhiro Nemoto
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Article
| Open AccessCharacterization of elusive rhamnosyl dioxanium ions and their application in complex oligosaccharide synthesis
Characterizing highly-reactive glycosyl cation intermediates and understanding their glycosylation mechanisms are essential to the stereoselective synthesis of complex carbohydrates. Here the authors report a workflow that is utilized to characterize rhamnosyl 1,3-bridged dioxanium ions derived from C-3 p-anisoyl esterified donors.
- Peter H. Moons
- , Floor ter Braak
- & Thomas J. Boltje
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Article
| Open AccessStabilization of N6 and N8 anionic units and 2D polynitrogen layers in high-pressure scandium polynitrides
The authors discover high-pressure Sc2N6, Sc2N8, and ScN5 polynitrides, synthesized at high pressure and temperature conditions, featuring a unique nitrogen catenation and previously unknown N66− anions, N86− anions and anionic corrugated 2D-polynitrogen layers.
- Andrey Aslandukov
- , Alena Aslandukova
- & Leonid Dubrovinsky
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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 AccessDimethyl sulfate and diisopropyl sulfate as practical and versatile O-sulfation reagents
O-Sulfation is a vital post-translational modification in bioactive molecules, yet there are significant challenges for the synthesis. Here, the authors report a general and robust approach to O-sulfation by harnessing the tunable reactivity of dimethyl sulfate or diisopropyl sulfate under tetrabutylammonium bisulfate activation.
- Shuaishuai Yue
- , Guoping Ding
- & Jiakun Li
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Article
| Open AccessGeneral alkyl fluoride functionalization via short-lived carbocation-organozincate ion pairs
Many alkyl fluorides are readily available, but the synthetic applications trail behind the widely accepted utility of other halides. Here, the authors report a practical Csp3-F bond functionalization method that expands the currently restricted synthetic space of unactivated C(sp3)-F bonds, but also uses benzylic, propargylic and acyl fluorides.
- D. Lucas Kane
- , Bryan C. Figula
- & Christian Wolf
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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 AccessMirror-image ligand discovery enabled by single-shot fast-flow synthesis of D-proteins
Mirror-image phage display has the potential for high-throughput generation of biologically stable macrocyclic D-peptide binders but is hindered by the optimization required for D-protein chemical synthesis. Here, the authors report a general mirror-image phage display pipeline based on automated flow peptide synthesis and use it to prepare and characterize 12 L/D-protein pairs.
- Alex J. Callahan
- , Satish Gandhesiri
- & Bradley L. Pentelute
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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 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 AccessSpontaneous crystallization of strongly confined CsSnxPb1-xI3 perovskite colloidal quantum dots at room temperature
Photoactive pure-iodine all-inorganic colloidal perovskite quantum dots (QDs) are attractive for optoelectronic applications, however their synthesis at room temperature is challenging. Here the authors report a room temperature strongly confined strategy to synthesize CsSnxPb1-xI3 QDs.
- Louwen Zhang
- , Hai Zhou
- & Guojia Fang
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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 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
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Article
| Open AccessCircular olefin copolymers made de novo from ethylene and α-olefins
Although several advances have been made in chemical Polyethylene (PE) re- and upcycling, energy-efficient and selective catalytic processes are still lacking. Here, the authors show coupling of an industrially relevant coordination copolymerization olefins with a functionalized chain-transfer agent, followed by modular assembly of the resulting telechelic polyolefin building blocks by polycondensation to afford ester-linked PE-based random and block copolymers which exhibit full chemical circularity.
- Xing-Wang Han
- , Xun Zhang
- & Yong Tang
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Article
| Open AccessOxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy
Direct use of flue gas for the electrocatalytic CO2 reduction reaction is desirable but severely limited by the thermodynamically favorable oxygen reduction reaction. Here the authors report an oxygen passivation strategy to improve electrocatalytic CO2 reduction reaction under aerobic conditions using a covalent organic frameworks with a photoswitching unit.
- Hong-Jing Zhu
- , Duan-Hui Si
- & Yuan-Biao Huang
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Article
| Open AccessAccessing ladder-shape azetidine-fused indoline pentacycles through intermolecular regiodivergent aza-Paternò–Büchi reactions
Conformationally rigid 3D molecules are of high interest. Here the authors develop intermolecular aza-Paternò-Büchi reactions to access ladder-shape azetidine-fused indoline pentacycles with excellent regiodivergency and stereoselectivity.
- Jianjian Huang
- , Tai-Ping Zhou
- & Fangrui Zhong
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Perspective
| Open AccessPerformance metrics to unleash the power of self-driving labs in chemistry and materials science
Assessing the performance of self-driving labs (SDLs) is challenging due to the specificities of each experiment. In this Perspective, the authors review recent literature of SDLs for materials science and chemistry and suggest how to report SDL performance more effectively.
- Amanda A. Volk
- & Milad Abolhasani
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