Reaction mechanisms articles within Nature Communications

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• Article
  06 March 2017 | Open Access

  Synthesis and structures of gold and copper carbene intermediates in catalytic amination of alkynes

  Metal carbenes are typically highly reactive and unstable species, proposed as intermediates in numerous catalytic processes. Here the authors report the isolation and characterization of gold and copper carbene intermediates involved in catalytic cyclization reactions.

  • Jiwei Wang
  • , Xiaoming Cao
  •  & Jun Zhang

• Article
  22 February 2017 | Open Access

  Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

  The H+CH₄substitution reaction is the simplest reaction occurring via the Walden inversion mechanism. Here, the authors perform a theoretical study of the reaction and uncover the important effect of the umbrella motion of the non-reacting methyl group on the reaction dynamics.

  • Zhiqiang Zhao
  • , Zhaojun Zhang
  •  & Dong H Zhang

• Article
  17 November 2016 | Open Access

  Near-infrared uncaging or photosensitizing dictated by oxygen tension

  The generation of reactive oxygen species (ROS) in photodynamic cancer treatments is limited by low intraturmoural oxygen availability. Here the authors show that irradiation of a silicon phthalocyanine leads to uncaging of a biologically active molecule or to ROS formation in an oxygen-dependent manner.

  • Erin D. Anderson
  • , Alexander P. Gorka
  •  & Martin J. Schnermann

• Article
  14 November 2016 | Open Access

  Deoxyfluorination of alcohols with 3,3-difluoro-1,2-diarylcyclopropenes

  Fluorination of organic molecules can dramatically change the properties and is commonly used for the synthesis of bioactive molecules. Here, the authors report the deoxyfluorination of alcohols and the selective monofluorination of diols using bench stable, tunable difluorocyclopropene reagents.

  • Lingchun Li
  • , Chuanfa Ni
  •  & Jinbo Hu

• Article
  11 November 2016 | Open Access

  Product lambda-doublet ratios as an imprint of chemical reaction mechanism

  Propensity for a given Λ-doublet level is a common feature in many chemical reactions, but has so far remained unexplained. Here, the authors show how to predict computationally those propensities and relate them to the reaction mechanism on concurrent potential energy surfaces.

  • P. G. Jambrina
  • , A. Zanchet
  •  & F. J. Aoiz

• Article
  06 October 2016 | Open Access

  Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene

  Baird’s rules say that the first triplet state of benzene displays antiaromatic character. Here, the authors exploit this to show that aromatic molecules can undergo rapid transfer hydrogenation or silylations without the need for metal catalysts when photochemcially excited into this state.

  • Raffaello Papadakis
  • , Hu Li
  •  & Henrik Ottosson

• Article
  30 September 2016 | Open Access

  Stille coupling via C–N bond cleavage

  The Stille reaction is a long-standing method for the construction of carbon-carbon bonds by coupling aryl halides with organotin compounds. Here the authors report a Stille coupling between aryl ammonium salts and arylstannanes catalysed by nickel.

  • Dong-Yu Wang
  • , Masatoshi Kawahata
  •  & Masanobu Uchiyama

• Article
  14 September 2016 | Open Access

  Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

  The Strecker reaction is a power method for the synthesis of cyano-substituted compounds. Here the authors report a dual-reagent system for asymmetric Strecker reactions, where an in situformed organocatalyst/methyl acrylate zwitterionic adduct activates both the cyanide source and the electrophile.

  • Hong-Yu Wang
  • , Chang-Wu Zheng
  •  & Gang Zhao

• Article
  10 August 2016 | Open Access

  Solvent-driven electron trapping and mass transport in reduced graphites to access perfect graphene

  Graphite intercalation compounds are promising precursors for the reductive exfoliation of graphene. Here, the authors unveil the discharging mechanism of reduced graphitic compounds in a solid/liquid phase reaction, and further demonstrate its practical use for graphene production.

  • Philipp Vecera
  • , Johannes Holzwarth
  •  & Andreas Hirsch

• Article
  05 July 2016 | Open Access

  Selective catalytic two-step process for ethylene glycol from carbon monoxide

  Conversion of one-carbon feedstocks to more complex structures is vital for the production of bulk chemicals. Here, the authors report a highly selective method for the conversion of carbon monoxide to ethylene glycol by means of an oxamide intermediate.

  • Kaiwu Dong
  • , Saravanakumar Elangovan
  •  & Matthias Beller

• Article
  20 June 2016 | Open Access

  Merging rhodium-catalysed C–H activation and hydroamination in a highly selective [4+2] imine/alkyne annulation

  C–H activations and hydroaminations are useful synthetic procedures for building up complex, functional molecules. Here, the authors report a single catalyst capable of performing tandem C–H activation and hydroamination, giving access to N-heterocycles via the [4+2] annulation of aromatic imines and alkynes.

  • Rajith S. Manan
  •  & Pinjing Zhao

• Article
  10 June 2016 | Open Access

  Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

  Palladium catalyzed allylic substitution reactions typically proceed via an outer sphere mechanism, yielding predominately linear products. Here, the authors report an inner sphere process for the allylic substitution of ketone enolates, giving branched products with up to three contiguous stereocentres.

  • Da-Chang Bai
  • , Fei-Le Yu
  •  & Xue-Long Hou

• Article
  10 June 2016 | Open Access

  Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction

  Transition metal dichalcogenides are promising hydrogen evolution catalysts however they can require expensive processing steps to enhance their activity. Here, the authors report a one-step activation step in which room temperature hydrazine treatment results in much enhanced electrocatalytic performance.

  • Dustin R. Cummins
  • , Ulises Martinez
  •  & Gautam Gupta

• Article
  10 June 2016 | Open Access

  Evidence for a chemical clock in oscillatory formation of UiO-66

  Reactions with non-linear kinetics, such as chemical clocks, are reasonably common but only well understood in the liquid phase. Here, the authors report and rationalize a chemical clock reaction taking place in a solidifying metal-organic framework.

  • M. G. Goesten
  • , M. F. de Lange
  •  & Jorge Gascon

• Article
  20 May 2016 | Open Access

  A two-step approach to achieve secondary amide transamidation enabled by nickel catalysis

  Transamidation reactions are kinetically and thermodynamically challenging because of the stability of the amide starting materials. Here, the authors show a two-step process—activation of a secondary amide, followed by nickel-catalysed C–N bond cleavage—that allows mild and high yielding transamidation.

  • Emma L. Baker
  • , Michael M. Yamano
  •  & Neil K. Garg

• Article
  11 May 2016 | Open Access

  Synthesis of acetic acid via methanol hydrocarboxylation with CO₂ and H₂

  Industrial routes to acetic acid use carbon monoxide for the carbonylation of methanol. Here, the authors report a hydrocarboxylation method that instead uses carbon dioxide and hydrogen for the conversion of methanol into acetic acid.

  • Qingli Qian
  • , Jingjing Zhang
  •  & Buxing Han

• Article
  09 May 2016 | Open Access

  Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy

  Non-equilibrium intercalation reactions may determine the performance of lithium-ion battery materials undergoing lithiation, but it is difficult to probe in real time. Here, the authors use in situelectron microscopy to identify kinetically-driven phase evolution in magnetite single nanoparticles.

  • Kai He
  • , Sen Zhang
  •  & Dong Su

• Article
  15 April 2016 | Open Access

  Enantioselective acyl transfer catalysis by a combination of common catalytic motifs and electrostatic interactions

  Nucleophilic catalysts are widely used for acyl transfer reactions, but chiral variants can be difficult to design or synthesise. Here, the authors report catalysts with chirality imparted from a binaphtyl moiety with tert-alcohol unit that show both high activity and enantioselectivity for a range of acyl transfer reactions.

  • Hiroki Mandai
  • , Kazuki Fujii
  •  & Seiji Suga

• Article
  01 April 2016 | Open Access

  Practical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation

  Olefins are employed in many coupling procedures but direct hydrocarbonations of unactivated olefins remain to be developed. Here, the authors report the nickel-catalyzed reductive coupling of olefins with aryl and alky electrophiles under mild conditions and with a broad substrate scope.

  • Xi Lu
  • , Bin Xiao
  •  & Lei Liu

• Article
  21 March 2016 | Open Access

  A strategy for sequence control in vinyl polymers via iterative controlled radical cyclization

  The ultimate control in polymer synthesis, precise monomer sequencing, is a highly sought after but complex problem. Here, the authors employ a repetitive and iterative intramolecular cyclization reaction, via a radical intermediate, to generate sequence-controlled vinyl oligomers.

  • Yusuke Hibi
  • , Makoto Ouchi
  •  & Mitsuo Sawamoto

• Article
  15 March 2016 | Open Access

  Metal-free intermolecular formal cycloadditions enable an orthogonal access to nitrogen heterocycles

  Nitrogen containing heterocycles play key roles as both bioactive compounds and synthetic building blocks in organic chemistry. Here, the authors report the synthesis of a range of heterocyclic structures via metal free cycloadditions and provide mechanistic analyses for the transformations.

  • Lan-Gui Xie
  • , Supaporn Niyomchon
  •  & Nuno Maulide

• Article
  19 February 2016 | Open Access

  A competitive and reversible deactivation approach to catalysis-based quantitative assays

  Assays for catalytic systems—particularly ones with simple colorimetric readouts—are useful for the rapid evaluation of performance. Here, the authors report an assay based on a concurrent colour-forming reaction working across a wide range that can be stopped to allow measurements and subsequently restarted.

  • Kazunori Koide
  • , Matthew P. Tracey
  •  & Christopher J. Welch

• Article
  05 February 2016 | Open Access

  Iron-catalysed cross-coupling of organolithium compounds with organic halides

  Cross coupling reactions of organolithiums are challenging due to their high reactivity, though palladium catalysed versions have been reported. Here, the authors report the cross coupling of organolithiums with aryl halides with inexpensive and widely available iron catalysts.

  • Zhenhua Jia
  • , Qiang Liu
  •  & Henry N. C. Wong

• Article
  11 December 2015 | Open Access

  Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis

  Acceptorless dehydrogenation of simple alkanes and alcohols provides useful functionality and typically requires precious metal catalysts. Here, the authors dehydrogenate unactivated alkanes and alcohols at room temperature using earth-abundant metals with hydrogen as the sole by-product.

  • Julian G. West
  • , David Huang
  •  & Erik J. Sorensen

• Article
  08 December 2015 | Open Access

  Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

  The formation of chiral centres adjacent to carbonyl groups is a highly challenging task in asymmetric catalysis. Here, the authors report the asymmetric diakylation of carbonyls via an intramolceular α-cyclopropanation procedure.

  • Chaosheng Luo
  • , Zhen Wang
  •  & Yong Huang

• Article
  21 October 2015 | Open Access

  Reversed reactivity of anilines with alkynes in the rhodium-catalysed C–H activation/carbonylation tandem

  C-H activation reactions allow transformations on relatively unfunctionalised organic molecules. Here, the authors describe rhodium-catalysed C-H bond activation of unprotected anilines with alkynes leading to C-C bond formation (rather than the more usual C-N), and subsequent annulation to form quinolines.

  • Siba P. Midya
  • , Manoj K. Sahoo
  •  & Ekambaram Balaraman

• Article
  16 October 2015 | Open Access

  High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

  Supported metal nanoparticles have been widely used as heterogeneous catalysts. Here, the authors report the synthesis of (1.1.1) copper on few layer graphene which oxidize to orientated (2.0.0) copper(I) oxide nanoplatelets which display high catalytic activity for a number of organic coupling reactions.

  • Ana Primo
  • , Ivan Esteve-Adell
  •  & Hermenegildo García

• Article
  07 October 2015 | Open Access

  Formation of oligopeptides in high yield under simple programmable conditions

  Typically, in order to form large peptides, complex procedures or activating agents are required. Here, the authors show that simple aqueous conditions with dehydration-hydration cycles are sufficient for the oligomerization of amino acids into peptides (up to 20 amino acids long) in yields of up to 50%.

  • Marc Rodriguez-Garcia
  • , Andrew J. Surman
  •  & Leroy Cronin

• Article
  29 September 2015 | Open Access

  Coordinating activation strategy for C(sp³)–H/C(sp³)–H cross-coupling to access β-aromatic α-amino acids

  Oxidative coupling of two C(sp3)-H groups is an attractive approach for the formation of carbon-carbon bonds, building structural complexity while avoiding the formation of waste salts. Here, the authors report such a transformation, using a nickel catalyst to functionalise amino acids with benzylic radicals.

  • Kaizhi Li
  • , Qian Wu
  •  & Jingsong You

• Article
  18 September 2015 | Open Access

  Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework

  Nanospace defined by unsaturated metal coordination sites opens up the possibility of controlling and templating chemical reactivity. Here, the authors show that a Fe(III) dicarboxylate framework with triangularly arranged metal sites can direct the [2+2+2] cyclisation of nitriles, alkynes and alkenes.

  • Yong-Sheng Wei
  • , Mei Zhang
  •  & Xiao-Ming Chen

• Article
  04 September 2015 | Open Access

  Non-covalent synthesis of supermicelles with complex architectures using spatially confined hydrogen-bonding interactions

  Ubiquitous in nature, hierarchical architectures are less commonly achieved in synthetic functional materials. Here, the authors design and carefully assemble block copolymer micelles into complex supermicelles using hydrogen bonding in orthogonal combination with other non-covalent interactions.

  • Xiaoyu Li
  • , Yang Gao
  •  & Ian Manners

• Article
  28 August 2015 | Open Access

  Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids

  Many structurally diverse carboxylic acids are available from renewable and petrochemical sources. Here, the authors report a method to reduce carboxylic acids to alcohols using hydrogen, with high selectivity, wherein the carboxylates form active and hydrogen-accepting parts of the catalyst system.

  • Masayuki Naruto
  •  & Susumu Saito

• Article
  10 August 2015 | Open Access

  A scalable and operationally simple radical trifluoromethylation

  Trifluoromethylation is a key transformation, particularly for pharmaceuticals, but many reagents are expensive and difficult to scale up. Here, the authors show that trifluoroacetic anhydride can act as a CF₃source, allowing the radical reactions to be easily and inexpensively carried out at scale.

  • Joel W. Beatty
  • , James J. Douglas
  •  & Corey R. J. Stephenson

• Article
  15 June 2015 | Open Access

  1,3,2,5-Diazadiborinine featuring nucleophilic and electrophilic boron centres

  Boron atoms in aromatic heterocycles typically behave simply as electron pair acceptors. Here, the authors report an aromatic system containing both electrophilic and nucleophilic boron atoms, and demonstrate how this imparts frustrated Lewis pair type reactivity, including binding of carbon dioxide.

  • Di Wu
  • , Lingbing Kong
  •  & Rei Kinjo

• Article
  01 June 2015 | Open Access

  Chemical reaction mechanisms in solution from brute force computational Arrhenius plots

  Obtaining activation entropies and enthalpies of a reaction is important for distinguishing between alternative reaction mechanisms. Here the authors use computational methods to accurately obtain the enthalpic/entropic components of the activation free energy for hydrolytic deamination reactions.

  • Masoud Kazemi
  •  & Johan Åqvist

• Article
  24 April 2015 | Open Access

  Radiolysis as a solution for accelerated ageing studies of electrolytes in Lithium-ion batteries

  The degradation of organic solvents used in lithium-ion batteries reduces battery performance. Here, the authors present a radiolysis technique which is not only more efficient than conventional thermally activated ageing methods, but also allows mechanistic analysis of the degradation process.

  • Daniel Ortiz
  • , Vincent Steinmetz
  •  & Sophie Le Caër

• Article
  22 April 2015 | Open Access

  Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

  Cascade and multi-component reactions allow highly functionalized molecules to be built from simpler precursors. Here, the authors report a three-component coupling giving α-amino-α-aryl ketones, initiated by the regioselective addition of nitrogen radicals to alkynes.

  • Guangfan Zheng
  • , Yan Li
  •  & Qian Zhang

• Article
  10 March 2015 | Open Access

  Cobalt-catalysed site-selective intra- and intermolecular dehydrogenative amination of unactivated sp³ carbons

  Functionalizing unactivated carbon–hydrogen bonds is challenging, especially when using non-precious metals and dealing with sp³ hybridized carbons. Here, the authors report an intramolecular cobalt catalysed amination of C–H bonds of sp³carbons, giving access to β- and γ-lactams.

  • Xuesong Wu
  • , Ke Yang
  •  & Haibo Ge

• Article | 23 February 2015

  Direct and selective hydrogenolysis of arenols and aryl methyl ethers

  Deoxygenating phenols is a difficult task, made more complex by the tendency of hydrogenation techniques to also reduce the aromatic ring. Here, the authors show an iridium catalyst that can selectively cleave the C–O bond in phenols and related compounds, as well as cleaving aryl methyl ethers.

  • Shuhei Kusumoto
  •  & Kyoko Nozaki

• Article | 19 January 2015

  Revealing a double-inversion mechanism for the F⁻+CH₃Cl S_N2 reaction

  The S_N2 reaction is a stereospecific process, normally occurring via back-side inversion or front-side retention. Here, the authors report a global potential energy surface for the reaction between fluoride and CH₃Cl and identify an additional double inversion mechanism.

  • István Szabó
  •  & Gábor Czakó

• Article
  14 January 2015 | Open Access

  Bond cleavage, fragment modification and reassembly in enantioselective three-component reactions

  Multi-component reactions allow complex structures to be rapidly built from simple starting materials. Here, the authors report an enantioselective three-component coupling of imines, enamines and aryldiazoacetates catalysed by a phosphinic acid and palladium(II).

  • Dan Zhang
  • , Jun Zhou
  •  & Wenhao Hu

• Article | 08 December 2014

  Asymmetric total synthesis of (−)-lingzhiol via a Rh-catalysed [3+2] cycloaddition

  Bicyclic rings with quaternary bridgehead positions are difficult targets, yet are frequently observed in nature. Here, the authors report a cycloaddition reaction giving access to these structures in a stereoselective manner and employ it as the key step in a natural product total synthesis.

  • Rong Long
  • , Jun Huang
  •  & Zhen Yang

• Article | 21 November 2014

  Asymmetric trapping of zwitterionic intermediates by sulphur ylides in a palladium-catalysed decarboxylation-cycloaddition sequence

  Sulphur ylides are useful reagents in organic synthesis, typically reacting with highly polar reagents. Here, the authors show a catalytic asymmetric process for the addition of sulphur ylides to cyclic allylic esters with loss of CO₂, giving access to chiral, highly functionalised indolines.

  • Tian-Ren Li
  • , Fen Tan
  •  & Wen-Jing Xiao

• Article | 18 November 2014

  Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

  Chiral heterocyclic compounds are highly valuable due to their biological and synthetic utility. Here the authors report a stereospecific cross-coupling methodology for the synthesis of non-aromatic heterocycles, giving products in high enantiomeric excess with control over the regioselectivity of bond formation.

  • Jinyue Ding
  • , Taras Rybak
  •  & Dennis G. Hall

• Article | 03 October 2014

  The intriguing dual-directing effect of 2-cyanobenzyl ether for a highly stereospecific glycosylation reaction

  Glycosylation reactions can be hampered by a lack of selectivity, giving mixtures of α- and β-products. Here, the authors demonstrate the use of 2-cyanobenzyl functionalization as a directing group to give α- or β-selectivity from a single starting material.

  • Kim Le Mai Hoang
  •  & Xue-Wei Liu

• Article | 22 July 2014

  Intramolecular C–F and C–H bond cleavage promoted by butadienyl heavy Grignard reagents

  Grignard reagents are one of the mainstays of organic synthesis, but analogues with other Group 2 metals (heavy Grignards) are less easy to control. Here, the authors generate butadienyl calcium and barium heavy Grignards and control their reactivity in C–F and C–H cleavage reactions.

  • Heng Li
  • , Xiao-Ye Wang
  •  & Zhenfeng Xi

• Article | 26 June 2014

  The Barbier–Grignard-type arylation of aldehydes using unactivated aryl iodides in water

  The Barbier–Grignard reaction is a commonly used method for forming carbon–carbon bonds, but for many substrates it is carried out in organic solvents. Here, the authors show a procedure for carrying out the reaction with unactivated aryl halides in water.

  • Feng Zhou
  •  & Chao-Jun Li

• Article | 06 June 2014

  Roaming dynamics in radical addition–elimination reactions

  Roaming dynamics have been shown to be important in unimolecular decompositions, but the relevance to bimolecular reactions has been less clear. Here, the authors study radical addition/elimination reactions and implicate a roaming transition state in a bimolecular reaction.

  • Baptiste Joalland
  • , Yuanyuan Shi
  •  & Alexander M. Mebel

• Article
  08 January 2014 | Open Access

  A Diels–Alder super diene breaking benzene into C₂H₂ and C₄H₄ units

  The stability of the benzene molecule reduces its tendency to react in ways that perturb the aromaticity—for example, in Diels–Alder reactions. Here the authors report a diene capable of not only inducing benzene to react under mild conditions but also of breaking apart the ring system itself.

  • Yusuke Inagaki
  • , Masaaki Nakamoto
  •  & Akira Sekiguchi

• Article | 12 September 2013

  Directing reaction pathways by catalyst active-site selection using self-assembled monolayers

  Control of active sites of heterogeneous catalysts can lead to enhanced product selectivity. Here, the authors use self-assembled alkanethiolate monolayers with varying surface densities to tune the selectivity of hydrogenation and hydrodeoxygenation of furfural on supported palladium catalysts.

  • Simon H. Pang
  • , Carolyn A. Schoenbaum
  •  & J. Will Medlin