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| Open AccessNHC-catalyzed enantioselective access to β-cyano carboxylic esters via in situ substrate alternation and release
The search for efficient methods for the enantioselective synthesis of cyano-containing molecules is important but synthesis methods are often limited by the need of toxic cyano salts or reduction with hydrogen gas. Here the authors report the efficient and selective access to β-cyano carboxylic esters which can be easily converted into γ-aminobutyric acid derivatives with high optical purities.
- Qingyun Wang
- , Shuquan Wu
- & Yonggui Robin Chi
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Article
| Open AccessPhotoredox cobalt-catalyzed regio-, diastereo- and enantioselective propargylation of aldehydes via propargyl radicals
Catalytic enantioselective introduction of a propargyl group is an important carbon–carbon forming reactions but only few Cu- or Ni-catalyzed protocols with limited reaction modes are known. Here, the authors describe a photoredox/cobalt-catalyzed propargyl addition to aldehydes via propargyl radicals which enables the construction of a broad scope of homopropargyl alcohols.
- Lei Wang
- , Chuiyi Lin
- & Fanke Meng
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Article
| Open AccessDiastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis
Axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active compounds but asymmetric synthesis of N-arylpyrroles is challenging. Here, the authors develop a diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis.
- Lei Dai
- , Xueting Zhou
- & Yixin Lu
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Article
| Open AccessModular assembly of indole alkaloids enabled by multicomponent reaction
Indole alkaloids are one of the largest alkaloid classes, proving valuable structural moiety in pharmaceuticals but the direct single-step synthesis with broad structural diversity remains challenging. Herein, the authors report a modular assembly of tetrahydrocarboline type of indole alkaloids from simple building blocks in a single step while showing broad compatibility with medicinally relevant functionality
- Jiaming Li
- , Zhencheng Lai
- & Sunliang Cui
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Article
| Open AccessCopper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of 1,3-enynes and azomethine ylides
One of the most efficient method to access chiral poly-substituted pyrrolidines is the catalytic asymmetric 1,3-dipolar cycloaddition, but using this reaction with weakly activated alkenes remains elusive. Here, the authors disclose a copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides and 1,3-enynes.
- Bo-Ran Wang
- , Yan-Bo Li
- & Liang Yin
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Article
| Open AccessRhodium-catalyzed enantioselective and diastereodivergent access to diaxially chiral heterocycles
Molecules with axial chirality are of intense focus to the synthetic organic community, but the axes most commonly explored are carbon–carbon and carbon–heteroatom. Here the authors report the syntheses of diaxially chiral biaryls containing N-N and C-N/C-C axes, achieved via rhodium catalysis.
- Yishou Wang
- , Xiaohan Zhu
- & Xingwei Li
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Article
| Open AccessValve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Here, the authors report an on-cycle mechanism for CoCl2bpy2 catalyzed Negishi-type cross-coupling describing a full catalytic cycle for this reaction using multiple spectroscopic studies.
- Xu Luo
- , Dali Yang
- & Aiwen Lei
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Article
| Open AccessNitroalkanes as thioacyl equivalents to access thioamides and thiopeptides
Replacement of oxoamide units with thioamides in peptide therapeutics is a valuable tactic to improve biological activity and resistance to enzymatic hydrolysis. Here, the authors develop a direct coupling of readily available nitroalkane and amines with elemental sulfur and base and provide an efficient way to form thioamides and thiopeptides.
- Xiaonan Wang
- , Silong Xu
- & Jing Li
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Article
| Open AccessSelective nucleophilic α-C alkylation of phenols with alcohols via Ti=Cα intermediate on anatase TiO2 surface
The authors report selective nucleophilic α-C alkylation of phenols with alcohols catalyzed by anatase titanium dioxide. Experimental and computational studies reveal the formation of Ti=Cα intermediate with the primary carbon of alkyl group at oxygen vacancies of anatase titanium dioxide.
- Xinze Du
- , Hongjun Fan
- & Z. Conrad Zhang
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Article
| Open AccessA photochemical method to evidence directional molecular motions
Light driven synthetic molecular motors represent crucial building blocks for advanced molecular machines and their applications but the development of very fast motors remains challenging. Here the authors restrict fast molecular motor rotations and force them to proceed in two separate rotation-photoequilibria enabling them to elucidate the directionality of the motion.
- Benjamin Lukas Regen-Pregizer
- , Ani Ozcelik
- & Henry Dube
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Article
| Open AccessElectrochemical synthesis of biaryls by reductive extrusion from N,N’-diarylureas
The synthesis of biaryls by transition metal-free coupling is an important challenge. Here, the authors describe an electrochemical approach to the synthesis of biaryls, in which aniline derivatives are coupled through the temporary formation and reduction of ureas.
- Ellie Stammers
- , Chris D. Parsons
- & Alastair J. J. Lennox
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Article
| Open AccessElectrochemical oxo-functionalization of cyclic alkanes and alkenes using nitrate and oxygen
Hydrocarbons are challenging to functionalize. Here, the authors present an electrochemical oxo-functionalization of cyclic alkanes and alkenes to ketones and dicarboxylic acids via mediating nitrate-based supporting electrolyte and molecular oxygen.
- Joachim Nikl
- , Kamil Hofman
- & Siegfried R. Waldvogel
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Article
| Open AccessConstruction of C-B axial chirality via dynamic kinetic asymmetric cross-coupling mediated by tetracoordinate boron
The application of catalytic dynamic kinetic asymmetric transformation (DyKAT) in axial chirality is limited to fivemembered metalacyclic intermediate-directed equilibrium of substrate enantiomers. Here, the authors report a tetracoordinate boron-directed DyKAT of racemic, configurationally stable 3-bromo- 2,1-azaborines for the construction of C-B axial chirality.
- Kai Yang
- , Yanfei Mao
- & Qiuling Song
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Article
| Open AccessDiversity-oriented synthesis of P-stereogenic and axially chiral monodentate biaryl phosphines enabled by C-P bond cleavage
Chiral monodentate biaryl phosphines (MOPs) have attracted intense attention as chiral ligands over the past decades. Here, the authors show diversity-oriented synthesis of structurally diverse MOPs containing both phosphorus and axial chirality.
- Liangzhi Pang
- , Zhan Huang
- & Qiankun Li
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Article
| Open AccessUnlocking full and fast conversion in photocatalytic carbon dioxide reduction for applications in radio-carbonylation
While the reduction of CO2 to CO is a very active research topic, use of the reduced CO in organic synthesis is not yet mature. Herein, the authors report a photocatalytic process that unlocks full CO2-to-CO conversion, opening opportunities for access to 11C- and 14C-labeled pharmaceuticals.
- Serena Monticelli
- , Alex Talbot
- & Davide Audisio
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Article
| Open AccessCarbene-catalyzed chemoselective reaction of unsymmetric enedials for access to Furo[2,3-b]pyrroles
Chemoselective reactions of two or multiple functional groups with similar reactivities remain an ongoing challenge in chemistry. Here the authors disclosed a chemoselective reaction of enedial and observed that the high chemoselectivity is mainly controlled via redox (rather than steric) properties of the substrate/catalyst.
- Guodong Fan
- , Qingyun Wang
- & Yonggui Robin Chi
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Article
| Open AccessElectrocatalyzed direct arene alkenylations without directing groups for selective late-stage drug diversification
Electrochemistry has emerged as an increasingly viable tool in molecular synthesis. Here the authors realize electrocatalyzed C−H activations, with the aid of data science and artificial intelligence, towards selective alkenylations for late-stage drug diversifications.
- Zhipeng Lin
- , Uttam Dhawa
- & Lutz Ackermann
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Article
| Open AccessKetones from aldehydes via alkyl C(sp3)−H functionalization under photoredox cooperative NHC/palladium catalysis
Direct synthesis of ketones from aldehydes features high atom- and step-economy. Here, the authors develop two- and three-component reactions for the synthesis of ketones from aldehydes via alkyl C(sp3)-H functionalization under photoredox cooperative NHC/Pd catalysis.
- Hai-Ying Wang
- , Xin-Han Wang
- & Song Ye
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Article
| Open AccessEfficient and versatile formation of glycosidic bonds via catalytic strain-release glycosylation with glycosyl ortho−2,2-dimethoxycarbonylcyclopropylbenzoate donors
Catalytic glycosylation provides access to oligosacchairdes with minimal amount of promoters. Here, the authors developed a new catalytic glycosylation reaction using an ester type donor driven by ring-strain release.
- Han Ding
- , Jian Lyu
- & Xue-Wei Liu
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Article
| Open AccessPhotoswitchable dynamic conjugate addition-elimination reactions as a tool for light-mediated click and clip chemistry
Photoinduced dynamic covalent bonds have the advantage of light-mediated bond making and breaking. Here, the authors report photoswitchable dynamic conjugate addition-elimination reactions with a broad scope and demonstrate diverse applications.
- Hanwei Lu
- , Hebo Ye
- & Lei You
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Article
| Open AccessTunably strained metallacycles enable modular differentiation of aza-arene C–H bonds
The ability to selectively functionalize different sites on simple starting materials is a constant pursuit in organic chemistry. Here, the authors report a catalytic system to regioselectively differentiate and alkynylate different positions on azaarenes via rhodium catalysis.
- Longlong Xi
- , Minyan Wang
- & Zhuangzhi Shi
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Article
| Open AccessAssembly drives regioselective azide-alkyne cycloaddition reaction
Metal-free versions of azide–alkyne cycloadditions could find widespread applications in biomedical contexts. Here, the authors report an assembly-driven, regioselective azide–alkyne cycloaddition.
- Qiaochu Jiang
- , Wenjun Zhan
- & Gaolin Liang
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Article
| Open AccessPhotoredox-catalyzed diastereoselective dearomative prenylation and reverse-prenylation of electron-deficient indole derivatives
Prenylated and reverse-prenylated indoline alkaloids are widely present in nature. Here, the authors demonstrate a tandem photoredox radical dearomatization/Claisen rearrangement of electron-deficient indoles for the rapid assembly of these privileged scaffolds.
- Xuexue Chang
- , Fangqing Zhang
- & Yangbin Liu
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Article
| Open AccessA 13-million turnover-number anionic Ir-catalyst for a selective industrial route to chiral nicotine
The development of catalysts for practical asymmetric hydrogenation of ketones remains an important goal of synthetic organic chemistry. Here, an anionic iridium catalyst with excellent activity is reported and used in a hundred-kilogram-scale reduction as part of a route to chiral nicotine.
- Congcong Yin
- , Ya-Fei Jiang
- & Xumu Zhang
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Article
| Open AccessGold-catalyzed four-component multifunctionalization of alkynes
The development of selective multifunctionalization of alkynes is essential for organic synthesis with alkyne units as building blocks. Here the authors report a gold-catalyzed, four-component reaction that achieves the oxo-arylfluorination or oxo-arylalkenylation of internal aromatic or aliphatic alkynes
- Shangwen Fang
- , Jie Han
- & Jin Xie
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Article
| Open AccessReaction performance prediction with an extrapolative and interpretable graph model based on chemical knowledge
Predictive modelling remains a key challenge for designing synthetic transformations. Here, the authors develop a knowledge-based graph model to predict reaction yield and stereoselectivity, offering an extrapolative and interpretable approach for evaluating reaction performance.
- Shu-Wen Li
- , Li-Cheng Xu
- & Xin Hong
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Article
| Open AccessArylcarboxylation of unactivated alkenes with CO2 via visible-light photoredox catalysis
Despite the importance of polycyclic carboxylic acids and derivatives in various fields, general methods for the arylcarboxylation of alkenes with CO2 remain elusive. Here, the authors transform unactivated alkenes into high value-added polycyclic carboxylic acids and derivatives via visible-light photoredox-catalysis, using CO2 as the one-carbon feedstock.
- Wei Zhang
- , Zhen Chen
- & Da-Gang Yu
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Article
| Open AccessCatalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes
The asymmetric inverse-electron-demand oxa-Diels–Alder reaction (IODA) between activated α,β-unsaturated carbonyl compounds with highly polarized alkenes has been reported before but acroleins or simple alkenes were so-far rarely employed as substrates. Here, the authors study the catalytic asymmetric intermolecular IODA reaction between acroleins and simple alkenes.
- Lei Zeng
- , Shihan Liu
- & Lizhu Gao
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Article
| Open AccessChemoselectivity change in catalytic hydrogenolysis enabling urea-reduction to formamide/amine over more reactive carbonyl compounds
The selective transformation of a less reactive carbonyl moiety in the presence of more reactive ones can realize straightforward and environmentally benign chemical processes but such a transformation is highly challenging. Here, the authors report an Ir catalyst for the selective hydrogenolysis of urea derivatives, which are the least reactive carbonyl compounds, affording formamides and amines even in the presence of more reactive carbonyl groups such as ester.
- Takanori Iwasaki
- , Kazuki Tsuge
- & Kyoko Nozaki
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Article
| Open AccessTrichalcogenasupersumanenes and its concave-convex supramolecular assembly with fullerenes
Synthesis of buckybowls has remained challenging due to the inherent high strain induced by the curvature. Herein, the authors report the synthesis of two bowl-shaped polycyclic aromatics with three chalcogen atoms and three methylene groups embedded at the bay regions of hexa-peri-hexabenzocoronene and demonstrate guest host complexation with trithiasupersumanene.
- Yixun Sun
- , Xin Wang
- & Junfa Wei
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Article
| Open AccessSolution-processable polymers of intrinsic microporosity for gas-phase carbon dioxide photoreduction
This works presents a series of solution processable, conjugated polymers of intrinsic microporosity, which are used as photocatalysts for carbon dioxide reduction to carbon monoxide in the presence of hydrogen.
- Floriana Moruzzi
- , Weimin Zhang
- & Iain McCulloch
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Article
| Open AccessEnantioselective synthesis of chiral quinohelicenes through sequential organocatalyzed Povarov reaction and oxidative aromatization
Heterohelicenes are of increasing importance in materials science but organocatalytic enantioselective synthesis of these molecules remains challenging. Here, the authors synthesize enantioenriched 1-(3-indol)-quino[n]helicenes through chiral phosphoric acid-catalyzed Povarov reaction followed by oxidative aromatization and explore the photochemical and electrochemical properties of these compounds.
- Chengwen Li
- , Ying-Bo Shao
- & Xin Li
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Article
| Open AccessMigratory allylic arylation of 1,n-enols enabled by nickel catalysis
Allylic substitution reactions have emerged as a powerful tool for the construction of C − C/X bonds. Here, the authors develop a migratory strategy of allylic arylation under the catalysis of nickel and lanthanide triflate.
- Dan Zhao
- , Bing Xu
- & Can Zhu
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Article
| Open AccessKetone α-alkylation at the more-hindered site
Ketone α-alkylation at the more hindered site is challenging. Here, the authors report a highly regioselective nickel-catalysed allylic alkylation of unsymmetrical ketones at the more-hindered α-site with allylic alcohols.
- Ming-Ming Li
- , Tianze Zhang
- & Qi-Lin Zhou
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Article
| Open AccessCopper-catalyzed asymmetric C(sp3)-H cyanoalkylation of glycine derivatives and peptides
Incorporating cyanoalkyl moieties into amino acids and peptides is of interest for potential imaging and therapeutic purposes. Here, the authors developed a Cu-catalyzed asymmetric cyanoalkylation of glycine derivatives for the synthesis of α-cyanoalkylate amino acids and peptide modification.
- Rupeng Qi
- , Qiao Chen
- & Zhaoqing Xu
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Article
| Open AccessPalladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides
Acid chloride formation is generally limited to the chlorination of carboxylic acids. Here, the authors report a palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for the synthesis of various alkyl acid chlorides.
- Fei Wu
- , Bo Wang
- & Zheng-Hui Guan
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Article
| Open AccessThe double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles
Coordination of benzene by a tungsten complex can minimize the formation of oligomeric aromatic products in Friedel-Crafts Arylation. Here the authors show that coordinating benzene to tungsten through two carbons (dihapto-coordination) enables a rarely observed double protonation of the bound benzene, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.
- Justin T. Weatherford-Pratt
- , Jacob A. Smith
- & W. Dean Harman
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Article
| Open AccessCross-linked polyaniline for production of long lifespan aqueous iron||organic batteries with electrochromic properties
Aqueous iron batteries are safe and cost-effective candidates for large-scale energy storage. However, their long-term cycling stability is inadequate. Here, the authors propose a crosslinked polyaniline-based positive electrode for high-power aqueous iron batteries with electrochromic properties.
- Haiming Lv
- , Zhiquan Wei
- & Hongfei Li
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Article
| Open AccessRetention time prediction for chromatographic enantioseparation by quantile geometry-enhanced graph neural network
Chromatographic enantioseparation requires tedious trials to find proper experimental conditions. Here, the authors construct a deep learning model to predict retention times of chiral molecules and obtain the separation probability under given conditions.
- Hao Xu
- , Jinglong Lin
- & Fanyang Mo
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Article
| Open AccessDirect allylic acylation via cross-coupling involving cooperative N‑heterocyclic carbene, hydrogen atom transfer, and photoredox catalysis
The versatility and importance of β,γ-unsaturated ketones has been appreciated for a long time in synthesis and medicinal chemistry. Here, the authors use carboxylic acids and readily available olefins as substrates for transformations involving N‑heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for the synthesis of β,γ-unsaturated ketones.
- Xiaochen Wang
- , Rongxin Yang
- & Qingmin Wang
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Article
| Open AccessLigand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides
Accessing saturated stereogenic centers by asymmetric alkyl-alkyl formation is attractive yet challenging. Here, the authors develop a Ni-catalysed cross-coupling reaction of two alkyl halides enabled by the in-situ formation of alkyl zinc from one alkyl halide.
- Wen-Tao Zhao
- , Jian-Xin Zhang
- & Wei Shu
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Article
| Open AccessDirect conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
Efficient valorization of lignin, a sustainable source of functionalized aromatic products, would reduce dependence on fossil-derived feedstocks. Here, the authors directly transform lignin into valuable functionalized diaryl ethers in near-theoretical-maximum yields, using oxidative cross coupling under copper catalysis.
- Mingyang Liu
- & Paul J. Dyson
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Article
| Open AccessAsymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis
Enantioselective α-allylic allenylation of carbonyls is a straightforward approach to access chiral allenes that are of significant relevance as synthons and bio-active products. Here, the Luo group describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes, via a combined chiral primary amine and palladium catalyst system.
- Chang You
- , Mingying Shi
- & Sanzhong Luo
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Article
| Open AccessRehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time
Electrocyclic reactions proceed through critical geometries, which are known as pericyclic transition states in thermal reactions and pericyclic minima in photochemical reactions. Here, the authors image the structure of a pericyclic minimum in real time using a combination of ultrafast electron diffraction and ab initio dynamics simulations.
- Y. Liu
- , D. M. Sanchez
- & T. J. A. Wolf
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Article
| Open AccessFlattened 1D fragments of fullerene C60 that exhibit robustness toward multi-electron reduction
Fullerenes are compelling molecular materials, but the reason for their high robustness to multi-electron reduction is still debated. Here, the authors synthesize flattened 1D fragments of fullerene C60 with high robustness against multi-electron reduction.
- Masahiro Hayakawa
- , Naoyuki Sunayama
- & Aiko Fukazawa
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Article
| Open AccessComputational study on the catalytic control of endo/exo Diels-Alder reactions by cavity quantum vacuum fluctuations
Strong light-matter interactions are a pathway to chemical control at the molecular level. Here, authors theoretically show that an optical cavity allows to control catalysis, inhibition, and endo/exo stereoselectivity in Diels-Alder reactions.
- Fabijan Pavošević
- , Robert L. Smith
- & Angel Rubio
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Article
| Open AccessSwitching imidazole reactivity by dynamic control of tautomer state in an allosteric foldamer
Molecular biology achieves control over complex reaction networks by means of molecular systems that translate a chemical input into an orthogonal chemical output but the application of dynamic foldamers has been limited by the restriction to stereochemical changes that produce spectroscopic signals. Here, the authors present an artificial molecular translation device that converts a chemical input into an unrelated chemical output.
- David P. Tilly
- , Jean-Paul Heeb
- & Jonathan Clayden
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Article
| Open AccessNi-catalyzed mild hydrogenolysis and oxidations of C–O bonds via carbonate redox tags
Catalytic redox transformations of C–O bonds are pertinent to the valorization of oxygenated hydrocarbons, but typically rely on hazardous redox agents which bring about numerous drawbacks ranging from safety hazards to waste management. Here, the authors demonstrate that such reagents can be rendered redundant by catalytically harnessing internal C–H bonds as redox equivalents.
- Georgios Toupalas
- , Loélie Ribadeau-Dumas
- & Bill Morandi
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Article
| Open AccessC(alkyl)–C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction
Inert C–C bond cleavage remains a challenge in organic chemistry. Herein, the authors report a retro-Diels-Alder process via palladium catalysis to achieve selective C(alkyl)–C(vinyl) bond cleavage.
- Qingyang Zhao
- , Le Yu
- & Zheng-Hui Guan