Reaction mechanisms articles within Nature Communications

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  • Article
    | Open Access

    Understanding the dynamic evolution of the catalysts’ structure under reaction conditions is crucial in heterogeneous catalysis. Here the authors use ab initio molecular dynamics simulations to show an anomalous decrease in reaction free energies and barriers on dynamical sub-nanometer Au clusters supported on MgO(001).

    • Juan-Juan Sun
    •  & Jun Cheng

  • Article
    | Open Access

    Difluorocarbene is a versatile and efficient intermediate for fluorine incorporation. Here, the authors show that difluorocarbene can be oxidized to carbonyl fluoride and this process is confirmed in 18O-trifluoromethoxylation reactions, by observation of AgOCF3 species and theory.

    • Jiao Yu
    • , Jin-Hong Lin
    •  & Ji-Chang Xiao

  • Article
    | Open Access

    Nucleophiles cannot be directly reacted with enolates due to polarity mismatching. Here, the authors developed an umpolung strategy for the selective synthesis of α-alkoxy carbonyl compounds by reaction of iridium enolates with nucleophilic alcohols promoted by an iodine(III) reagent.

    • Amparo Sanz-Marco
    • , Samuel Martinez-Erro
    •  & Belén Martín-Matute

  • Article
    | Open Access

    Strong coupling of molecular vibrations to an optical cavity may catalyze thermally activated reactions, showcasing the potential of polariton chemistry. Here, the authors provide a theoretical framework explaining the chemical kinetics deriving from transit through polaritonic and dark states.

    • Jorge A. Campos-Gonzalez-Angulo
    • , Raphael F. Ribeiro
    •  & Joel Yuen-Zhou

  • Article
    | Open Access

    α-Fluoromethyl arenes are common substructures in pharmaceuticals and agrochemicals but synthetic routes are still rare. Here the authors describe Pd-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids affording structurally diverse α-fluorinated diarylmethanes.

    • Masakazu Nambo
    • , Jacky C.-H. Yim
    •  & Cathleen M. Crudden

  • Article
    | Open Access

    Polycyclic aromatic hydrocarbons (PAHs) represent key molecular building blocks in extraterrestrial environments but the understanding of their formation and growth in this environment has remained elusive. Here the authors reveal how naphthalene can be efficiently formed via rapid radical–radical reactions.

    • Long Zhao
    • , Ralf. I. Kaiser
    •  & Stanislaw F. Wnuk

  • Article
    | Open Access

    Conventionally, 1,2-dicarbonyl compounds are prepared via α-keto acyl chlorides. Here, the authors report a metal-free synthesis of α-ketothioester reagents via the combination of an α-hydroxyl ketone, elemental sulfur and a benzyl halide, which are used for N- or C-dicarbonyl bond formation.

    • Ming Wang
    • , Zhihong Dai
    •  & Xuefeng Jiang

  • Article
    | Open Access

    Tsuji–Trost allylation is a traditional method for selective C-C bond formation that involves the use of palladium-based catalysts. Here, the authors report a metal-free, photocatalytic allylation of several heterocycles, amines and alcohols, which can be easily tuned towards the Z- or E- allylated product.

    • Ana María Martínez-Gualda
    • , Rafael Cano
    •  & José Alemán

  • Article
    | Open Access

    Classical hydroacylation of alkenes with aldehydes is a straightforward route to ketones, however aldehyde decarbonylation is a common side-process. Here, the authors report the coupling of amides, as hydroacylating agents, and alkenes under mild, metal-free conditions to afford a wide range of ketones.

    • Jing Li
    • , Rik Oost
    •  & Nuno Maulide

  • Article
    | Open Access

    Zeolite-catalyzed dehydration of ethanol offers promising perspectives for the sustainable production of ethene, while the initial step of ethanol dehydration is still unclear. Here, the authors report the observation of a triethyloxonium ion intermediate in ethanol dehydration to ethene on H-ZSM-5 by using solid-state NMR spectroscopy.

    • Xue Zhou
    • , Chao Wang
    •  & Feng Deng

  • Article
    | Open Access

    α-Borylcarbonyl compounds are versatile synthons in organic synthesis, however their preparation is often tedious. Here, the authors report a regioselective radical α-borylation of α,β-unsaturated carbonyl compounds to afford α-borylcarbonyl molecules with high selectivity and functional group compatibility.

    • Shi-Chao Ren
    • , Feng-Lian Zhang
    •  & Yi-Feng Wang

  • Article
    | Open Access

    Simulating ultrafast quantum dissipation in molecular excited states is a strongly demanding computational task. Here, the authors combine tensor network simulation, entanglement renormalisation and machine learning to simulate linear vibronic models, and test the method by analysing singlet fission dynamics.

    • Florian A. Y. N. Schröder
    • , David H. P. Turban
    •  & Alex W. Chin

  • Article
    | Open Access

    Understanding how simple chemical mixtures transition into truly emergent systems is essential to create new lifelike materials. Here, the authors show a self-replicating system that can be maintained out-of-equilibrium by an oxidant fuel in analogy to simple metabolic cycles.

    • Sarah M. Morrow
    • , Ignacio Colomer
    •  & Stephen P. Fletcher

  • Article
    | Open Access

    CO2 conversion to reduced products provides a use for greenhouse gases, but reaction complexity stymies mechanistic studies. Here, authors present a microkinetic model for CO2 and CO reduction on copper, based on ab initio simulations, to elucidate pH’s impact on competitive reaction pathways.

    • Xinyan Liu
    • , Philomena Schlexer
    •  & Karen Chan

  • Article
    | Open Access

    Tautomerization of imines into enamines is the basis of their similar reactivity; however, minor structural changes may lead to different outcomes. Here, the authors show that the reaction of cyclohexanone and amines in presence of TEMPO affords either α-amino-enones or arylamines depending on the intermediate imine structure.

    • Xiaoming Jie
    • , Yaping Shang
    •  & Weiping Su

  • Article
    | Open Access

    The catalytic C(sp3)-CF2 bond formation is of high interest in drug design and discovery. Here, the authors report a cobalt-catalyzed difluoroalkylation of tertiary α-C-H bonds of aryl ketones for facile synthesis of quaternary alkyl difluorides and show the late-stage functionalization of marketed drugs.

    • Chao Li
    • , Yi-Xuan Cao
    •  & Xi-Sheng Wang

  • Article
    | Open Access

    Diversity-oriented synthesis is a valuable strategy to construct complex molecules of medicinal interest. Here, the authors show a folding cascade strategy to convert linear substrates into polycyclic compounds with multiple stereocentres by combining the reductive chemistry of SmI2 with 1,5-hydrogen atom transfer.

    • Mateusz P. Plesniak
    • , Monserrat H. Garduño-Castro
    •  & David J. Procter

  • Article
    | Open Access

    Understanding fundamental processes that occur using solar-to-fuel conversion materials is crucial for constructing effective renewable energy collection. Here, authors find the hydrogen peroxide light-driven hole-scavenging mechanism over haematite to proceed with two active sites rather than one

    • Yotam Y. Avital
    • , Hen Dotan
    •  & Arik Yochelis

  • Article
    | Open Access

    Strobilurins are fungal metabolites that inspired the creation of β-methoxyacrylate agricultural fungicides. Here, Nofiani et al. identify the strobilurin biosynthesis gene cluster, encoding a polyketide synthase as well as an FAD-dependent oxygenase for an oxidative rearrangement leading to β-methoxyacrylate formation.

    • Risa Nofiani
    • , Kate de Mattos-Shipley
    •  & Russell J. Cox

  • Article
    | Open Access

    Electrophilic acylation of arenes is largely limited to electron rich systems, non-polar medium and often displays moderate selectivity. Here, the authors show a directed para-selective ketonisation of arenes, overriding electronic bias and structural congestion, and apply it to the synthesis of bioactive compounds.

    • Arun Maji
    • , Amit Dahiya
    •  & Debabrata Maiti

  • Article
    | Open Access

    Chalcogen-containing compounds find broad application in chemical industry. Here, the authors report a nickel-catalyzed reductive chalcogenation of unactivated alkyl bromides with thiosulfonates and selenosulfonates to access a range of unsymmetrical sulfides and selenides under mild conditions.

    • Yi Fang
    • , Torben Rogge
    •  & Shun-Jun Ji

  • Article
    | Open Access

    Radical reactivity of diazo compounds, useful organic building blocks, is yet underexplored. Here, the authors report an iodine-catalyzed radical activation of diazo compounds affording a variety of substituted cyclopropanes, pyrroles and epoxides under either thermal- or photo-initiated conditions.

    • Pan Li
    • , Jingjing Zhao
    •  & Fuwei Li

  • Article
    | Open Access

    The current industrial ammonia synthesis relies on the Haber-Bosch process that is limited by the Brønsted–Evans–Polanyi relation. Here, the authors propose a new strategy that an anchored Fe3 on θ-Al2O3(010) surface serves as a heterogeneous single cluster catalyst for ammonia synthesis from first-principles calculations and microkinetic analysis.

    • Jin-Cheng Liu
    • , Xue-Lu Ma
    •  & Jun Li

  • Article
    | Open Access

    Despite being essential to organic chemistry, the curly arrow notation of reaction mechanisms has been treated with suspicion due to its unclear connection with quantum mechanics. Here, the authors show that analysis of wavefunction 'tiles' along a reaction coordinate reveals the electron motion depicted by curly arrows.

    • Yu Liu
    • , Philip Kilby
    •  & Timothy W. Schmidt

  • Article
    | Open Access

    Despite the biological importance of sulfones, available synthetic methods usually involve toxic metals and reagents or harsh conditions. Here, the authors report an environmentally benign procedure for the metal-free carbon-sulfur bond formation of allylic sulfones in neutral aqueous medium at room temperature.

    • Peizhong Xie
    • , Jinyu Wang
    •  & Teck-Peng Loh

  • Article
    | Open Access

    Selective para-functionalization of substituted arenes is a formidable challenge in homogeneous catalysis. Here, the authors achieved the para-selective C-H difluoromethylation of anilides, indolines and tetrahydroquinolines with a ruthenium catalyst in good yields and apply it to the synthesis of bioactive compounds.

    • Chunchen Yuan
    • , Lei Zhu
    •  & Yingsheng Zhao

  • Article
    | Open Access

    Catalytic methodologies that incorporate commodity chemicals ethylene and ethyne into fine chemicals are quite limited. Here, the authors show a cobalt-catalyzed electrochemical C-H/N–H [4+2] annulation of aryl/vinyl amides with ethylene or ethyne to produce N-heterocycles in absence of oxidants.

    • Shan Tang
    • , Dan Wang
    •  & Aiwen Lei

  • Article
    | Open Access

    Saturated N-heterocycle rings are common structural motifs of many FDA-approved drugs. Here, the authors show that a metal-free amphoteric diamination of allenes produces valuable six-, seven- and eight-membered N-heterocycles with high diversity and tolerance of functional groups on the ring.

    • Zhishi Ye
    • , Sarju Adhikari
    •  & Mingji Dai

  • Article
    | Open Access

    Synthesis of cyclopropanes bearing vicinal all-carbon quaternary stereocenters poses synthetic challenges. Here, the authors report an intramolecular radical cyclopropanation with a copper/amine cooperative catalytic system for the efficient construction of bicyclo[3.1.0]hexane skeletons, also enantioselectively.

    • Liu Ye
    • , Qiang-Shuai Gu
    •  & Xin-Yuan Liu

  • Article
    | Open Access

    The citric acid cycle (TCA) is a fundamental metabolic pathway to release stored energy in living organisms. Here, the authors report two linked cycles of reactions that each oxidize glyoxylate into CO2 and generate intermediates shared with the modern TCA cycle, shedding light into a plausible TCA protometabolism.

    • Greg Springsteen
    • , Jayasudhan Reddy Yerabolu
    •  & Ramanarayanan Krishnamurthy

  • Article
    | Open Access

    Metal-carbon σ bonds mark the basis of organometallic chemistry, but the formation of multiple such bonds between single organic and metal entities remains a challenge. Here, the authors report a one-pot aromaticity-driven method to construct osmium-based multidentate complexes containing three metal-carbon σ bonds from multiyn chains.

    • Qingde Zhuo
    • , Jianfeng Lin
    •  & Haiping Xia

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