Articles

  • Article |

    Nickel complexes are of ever-increasing importance in organic synthesis; however, unstable Ni(COD)2 is still the main Ni(0) source used. Here the authors report a solution to this long-standing issue: an air stable Ni(0) complex that acts as a general precatalyst for numerous nickel-catalysed reactions.

    • Lukas Nattmann
    • , Rakan Saeb
    • , Nils Nöthling
    •  & Josep Cornella
  • Article |

    Methods to allow access to all isomers of a product are both valuable and challenging to achieve. Here the authors report a catalytic system comprised of an N-heterocyclic carbene and an iridium complex, and show that it can be used for the asymmetric, diastereodivergent synthesis of γ-butyrolactones.

    • Santanu Singha
    • , Eloisa Serrano
    • , Shobhan Mondal
    • , Constantin G. Daniliuc
    •  & Frank Glorius
  • Article |

    Additions to alkenes and alkynes are useful routes for generating highly functionalized products. Here the authors report the 1,1-difunctionalization of alkynes through a CuH-catalysed asymmetric hydroboration/hydroamination cascade.

    • De-Wei Gao
    • , Yang Gao
    • , Huiling Shao
    • , Tian-Zhang Qiao
    • , Xin Wang
    • , Brittany B. Sanchez
    • , Jason S. Chen
    • , Peng Liu
    •  & Keary M. Engle
  • Article |

    The sugar d-apiose is important in plant cell wall polysaccharides. Here the authors elucidate the complex, multistep biosynthetic pathway for its production using enzyme crystal structures and computational analysis.

    • Simone Savino
    • , Annika J. E. Borg
    • , Alexander Dennig
    • , Martin Pfeiffer
    • , Francesca De Giorgi
    • , Hansjörg Weber
    • , Kshatresh Dutta Dubey
    • , Carme Rovira
    • , Andrea Mattevi
    •  & Bernd Nidetzky
  • Article |

    The synthesis of organophosphorus compounds from elemental phosphorus is an inefficient process, using multiple steps, stoichiometric metal complexes and/or hazardous reagents such as chlorine gas. Here, a direct photocatalytic route to convert white phosphorus (P4) into phosphines and phosphonium salts is reported.

    • Ulrich Lennert
    • , Percia Beatrice Arockiam
    • , Verena Streitferdt
    • , Daniel J. Scott
    • , Christian Rödl
    • , Ruth M. Gschwind
    •  & Robert Wolf
  • Article |

    The synthesis of chiral amines is of crucial importance for the pharmaceutical industry, but it remains a challenging task and is often inefficient. Now, a heterogeneous iridium complex is developed for the asymmetric hydrogenation of imines and the asymmetric reductive amination of carbonyl compounds in continuous flow with high yields and enantioselectivities.

    • Tomohiro Yasukawa
    • , Ryusuke Masuda
    •  & Shū Kobayashi
  • Article |

    The electrocatalytic upgrading of CO to higher-value feedstocks provides a promising route to multicarbon products. Here, the authors show that high ethylene selectivity can be achieved by constraining CO availability on copper, with an ethylene Faradaic efficiency of 72% and a partial current density of >800 mA cm−2.

    • Jun Li
    • , Ziyun Wang
    • , Christopher McCallum
    • , Yi Xu
    • , Fengwang Li
    • , Yuhang Wang
    • , Christine M. Gabardo
    • , Cao-Thang Dinh
    • , Tao-Tao Zhuang
    • , Liang Wang
    • , Jane Y. Howe
    • , Yang Ren
    • , Edward H. Sargent
    •  & David Sinton
  • Article |

    The asymmetric hydrogenation of alkenes is a common route to optically active compounds, but alkene synthesis is often atom-inefficient, and the formation of isomers further complicates the procedure. Now the Ir-catalysed deoxygenation of racemic alcohols is shown to be a simple route to enantioenriched products.

    • Jia Zheng
    • , Jira Jongcharoenkamol
    • , Bram B. C. Peters
    • , Jasper Guhl
    • , Sudipta Ponra
    • , Mårten S. G. Ahlquist
    •  & Pher G. Andersson
  • Article |

    Photocatalytic activation of alkyl carbon–chlorine bonds has constantly proven difficult due to the high energies needed to cleave this stable bond. Here a surfactant-based photocatalytic system is used, allowing for the radical dehalogenation and subsequent reactivity of unactivated alkyl chlorides.

    • Maciej Giedyk
    • , Rok Narobe
    • , Sophia Weiß
    • , Didier Touraud
    • , Werner Kunz
    •  & Burkhard König
  • Article |

    Due to its stability nitrogen is often employed as an inert gas during catalytic reactions. Now, a study shows that N2 can act as promoter for the catalytic hydrodeoxygenation of p-cresol on supported ruthenium catalysts through the formation of hydrogenated nitrogen species acting as a source of protic hydrogen.

    • Haohong Duan
    • , Jin-Cheng Liu
    • , Ming Xu
    • , Yufei Zhao
    • , Xue-Lu Ma
    • , Juncai Dong
    • , Xusheng Zheng
    • , Jianwei Zheng
    • , Christopher S. Allen
    • , Mohsen Danaie
    • , Yung-Kang Peng
    • , Titipong Issariyakul
    • , Dongliang Chen
    • , Angus I. Kirkland
    • , Jean-Charles Buffet
    • , Jun Li
    • , Shik Chi Edman Tsang
    •  & Dermot O’Hare
  • Article |

    Deuterated molecules are important both as labelled probes and as targets in their own right. Here the authors report a very simple and general deuteration of aldehydes, by the use of an N-heterocyclic carbene catalyst in the presence of D2O.

    • Huihui Geng
    • , Xiaobei Chen
    • , Jingjing Gui
    • , Yueteng Zhang
    • , Zuyuan Shen
    • , Pengfei Qian
    • , Junwei Chen
    • , Shilei Zhang
    •  & Wei Wang
  • Article |

    This work shows that the biosynthesis of the polyether tetronasin involves an apparent enzyme-catalysed inverse-electron-demand hetero-Diels–Alder reaction to form an unexpected oxadecalin intermediate. A second enzyme then rearranges the oxadecalin to form the four-ringed tetronasin.

    • Rory Little
    • , Fernanda C. R. Paiva
    • , Robert Jenkins
    • , Hui Hong
    • , Yuhui Sun
    • , Yuliya Demydchuk
    • , Markiyan Samborskyy
    • , Manuela Tosin
    • , Finian J. Leeper
    • , Marcio V. B. Dias
    •  & Peter F. Leadlay
  • Article |

    To achieve large-scale application of water electrolysers we need to find optimal cathode and anode catalysts. This work reports an engineered silver catalyst with high density of stacking faults that exhibits high activity and stability for the hydrogen evolution reaction, outperforming commercial platinum on carbon.

    • Zhe Li
    • , Jian-Yu Fu
    • , Yi Feng
    • , Cun-Ku Dong
    • , Hui Liu
    •  & Xi-Wen Du
  • Article |

    Visualizing catalysts at work poses significant experimental challenges. Here, an operando scanning tunnelling microscopy study of the cobalt-catalysed Fischer–Tropsch synthesis is presented, which establishes steps as the active sites of the process by correlating activity under realistic conditions with step density.

    • Bernhard Böller
    • , Katharina M. Durner
    •  & Joost Wintterlin
  • Article |

    Selective functionalization of C(sp3)–H bonds is difficult in alkanes and other hydrocarbons, and especially so for enantioselective reactions. Here the authors report a photocatalyst and chiral metal catalyst to allow the radical, asymmetric addition of alkyl, allylic and benzylic groups to imines.

    • Yanjun Li
    • , Meng Lei
    •  & Lei Gong
  • Article |

    Reductive desymmetrization of 2,2-disubstituted cyclodiketones can provide valuable complex molecules with multiple chiral centres, but the generation of a single stereoisomer is difficult. This work addresses this synthetic challenge by engineering the activity and stereoselectivity of a carbonyl reductase.

    • Xi Chen
    • , Hongliu Zhang
    • , Miguel A. Maria-Solano
    • , Weidong Liu
    • , Juan Li
    • , Jinhui Feng
    • , Xiangtao Liu
    • , Sílvia Osuna
    • , Rey-Ting Guo
    • , Qiaqing Wu
    • , Dunming Zhu
    •  & Yanhe Ma
  • Article |

    Tackling the loss of expensive cofactors is a key challenge in continuous-flow biocatalysis. This work reports immobilized enzymes with a tethered cofactor that is channelled between a recycling and a catalysis module facilitating total turnover numbers of NAD+ and ATP exceeding 10,000 in biocatalytic flow systems.

    • Carol J. Hartley
    • , Charlotte C. Williams
    • , Judith A. Scoble
    • , Quentin I. Churches
    • , Andrea North
    • , Nigel G. French
    • , Tom Nebl
    • , Greg Coia
    • , Andrew C. Warden
    • , Greg Simpson
    • , Andrew R. Frazer
    • , Chantel Nixon Jensen
    • , Nicholas J. Turner
    •  & Colin Scott
  • Article |

    Simple enzyme mimetics are highly desired for industrial settings providing high catalyst stability and low production costs. This work reports that phenylalanine and zinc ions can self-assemble into a supramolecular structure showing catalytic properties similar to those of the natural enzyme carbonic anhydrase.

    • Pandeeswar Makam
    • , Sharma S. R. K. C. Yamijala
    • , Kai Tao
    • , Linda J. W. Shimon
    • , David S. Eisenberg
    • , Michael R. Sawaya
    • , Bryan M. Wong
    •  & Ehud Gazit
  • Article |

    Asymmetric routes for the formation of tetrasubstituted allenes are scarce and limited in scope. Now, a catalytic asymmetric process is reported giving access to tetrasubstituted allenes from readily available propargylic alcohols, and a potential role for an achiral supporting ligand is postulated.

    • Wei-Feng Zheng
    • , Wanli Zhang
    • , Chaofan Huang
    • , Penglin Wu
    • , Hui Qian
    • , Lei Wang
    • , Yin-Long Guo
    •  & Shengming Ma
  • Article |

    Enantioselective synthesis of atropisomeric biaryls is highly desirable due to the utility of these compounds as ligands and catalysts. Now, an organocatalytic polyketide cyclization is shown to convert poly-β-carbonyl compounds into binaphthalene derivatives in good enantioselectivities.

    • Reto M. Witzig
    • , Vincent C. Fäseke
    • , Daniel Häussinger
    •  & Christof Sparr
  • Article |

    Multi-modal approaches to simultaneously characterize different aspects of a reaction in situ are not readily accessible. Here, catalyst extrudates equipped with both luminescence thermometry and Raman spectroscopy sensors are introduced, providing an in-depth picture for the conversion of syngas on a supported rhodium catalyst.

    • Thomas Hartman
    • , Robin G. Geitenbeek
    • , Gareth T. Whiting
    •  & Bert M. Weckhuysen
  • Article |

    Due to its importance, the water-gas shift reaction has been the subject of numerous studies; however, a unifying mechanistic picture has not yet emerged. Now, a combination of spectroscopic, kinetic and computational methods reveal the crucial role of carboxyl intermediate for this centuries-old process.

    • Nicholas C. Nelson
    • , Manh-Thuong Nguyen
    • , Vassiliki-Alexandra Glezakou
    • , Roger Rousseau
    •  & János Szanyi
  • Article |

    Small changes in catalyst synthesis can have large and often poorly understood effects on activity. Here the authors show how variation of post synthetic heat treatment—in combination with changes in metal loadings—can lead to the most efficient catalysts, and also identify the most likely active sites.

    • Margherita Macino
    • , Alexandra J. Barnes
    • , Sultan M. Althahban
    • , Ruiyang Qu
    • , Emma K. Gibson
    • , David J Morgan
    • , Simon J. Freakley
    • , Nikolaos Dimitratos
    • , Christopher J. Kiely
    • , Xiang Gao
    • , Andrew M. Beale
    • , Donald Bethell
    • , Qian He
    • , Meenakshisundaram Sankar
    •  & Graham J. Hutchings
  • Article |

    Imine reductases have been regarded as one of the most promising enzymes by the pharmaceutical industry—but their industrial application is still lacking. This work reports the successful industrial application of an imine reductase, enabled by directed evolution.

    • Markus Schober
    • , Chris MacDermaid
    • , Anne A. Ollis
    • , Sandy Chang
    • , Diluar Khan
    • , Joseph Hosford
    • , Jonathan Latham
    • , Leigh Anne F. Ihnken
    • , Murray J. B. Brown
    • , Douglas Fuerst
    • , Mahesh J. Sanganee
    •  & Gheorghe-Doru Roiban
  • Article |

    Directed evolution typically requires extensive screening. This work presents an ultrahigh-throughput microfluidic assay, based on a coupled reaction and fluorescence-activated droplet sorting, enabling a 960-fold activity improvement of an amine oxidase for a non-natural substrate in a single round.

    • Aaron Debon
    • , Moritz Pott
    • , Richard Obexer
    • , Anthony P. Green
    • , Lukas Friedrich
    • , Andrew D. Griffiths
    •  & Donald Hilvert
  • Article |

    One of the major challenges in C–H functionalization is to achieve selectivity when multiple bonds of similar reactivity are present. Now, a method to selectively amidate sterically and electronically similar β- or γ-C–H bonds that utilize different silver catalysts is reported, giving access to valuable 1,2- and 1,3-aminoalcohols.

    • Minsoo Ju
    • , Minxue Huang
    • , Logan E. Vine
    • , Mahzad Dehghany
    • , Jessica M. Roberts
    •  & Jennifer M. Schomaker
  • Article |

    Targeted therapy is an important approach to reduce the side effects of medicinal drugs. This work reports the synthesis of catalytically active Pd nanostructures in exosomes that selectively target cancer cells for drug activation using biorthogonal chemistry.

    • María Sancho-Albero
    • , Belén Rubio-Ruiz
    • , Ana M. Pérez-López
    • , Víctor Sebastián
    • , Pilar Martín-Duque
    • , Manuel Arruebo
    • , Jesús Santamaría
    •  & Asier Unciti-Broceta
  • Article |

    Cu2O is a promising photocatalyst, although its stability is compromised by a disproportionation reaction that leads to the formation of Cu and CuO. Now, a method is reported to stabilize Cu2O nanocubes, rendering them highly active and stable for the photocatalytic reverse water–gas shift reaction.

    • Lili Wan
    • , Qixing Zhou
    • , Xin Wang
    • , Thomas E. Wood
    • , Lu Wang
    • , Paul N. Duchesne
    • , Jiuli Guo
    • , Xiaoliang Yan
    • , Meikun Xia
    • , Young Feng Li
    • , Abdinoor A. Jelle
    • , Ulrich Ulmer
    • , Jia Jia
    • , Tian Li
    • , Wei Sun
    •  & Geoffrey A. Ozin
  • Article |

    Performing photocatalytic CO2 reduction in a selective fashion with molecular catalysts represents a considerable challenge. Here, a binuclear cobalt complex featuring a bi-quaterpyridine ligand is developed that can selectively afford either carbon monoxide or formate by selection of the reaction medium acidity.

    • Zhenguo Guo
    • , Gui Chen
    • , Claudio Cometto
    • , Bing Ma
    • , Hongyan Zhao
    • , Thomas Groizard
    • , Lingjing Chen
    • , Hongbo Fan
    • , Wai-Lun Man
    • , Shek-Man Yiu
    • , Kai-Chung Lau
    • , Tai-Chu Lau
    •  & Marc Robert
  • Article |

    Traditional modes of catalyst deactivation such as Ostwald ripening and particle migration and coalescence eventually lead to sintering and particle growth. Now, Cargnello and colleagues identify loading-dependent particle decomposition into single atoms as an important deactivation mechanism during methane combustion on colloidal Pd nanocrystals.

    • Emmett D. Goodman
    • , Aaron C. Johnston-Peck
    • , Elisabeth M. Dietze
    • , Cody J. Wrasman
    • , Adam S. Hoffman
    • , Frank Abild-Pedersen
    • , Simon R. Bare
    • , Philipp N. Plessow
    •  & Matteo Cargnello
  • Article |

    The direct amination of alcohols with ammonia is a modern and clean route for the synthesis of amines. This joint theoretical and experimental study reveals the key factors governing the activity and selectivity to primary amines on metals, which are then used for the rational design of bimetallic catalysts.

    • Tao Wang
    • , Javier Ibañez
    • , Kang Wang
    • , Lin Fang
    • , Maarten Sabbe
    • , Carine Michel
    • , Sébastien Paul
    • , Marc Pera-Titus
    •  & Philippe Sautet
  • Article |

    Encapsulation is an effective strategy to tune metal-catalysed reactions, although its potential has not been fully explored. Here, design principles and advanced understanding of the reactivity of different polymer-encapsulated Pd nanocrystals are provided using CO oxidation as a benchmark reaction.

    • Andrew R. Riscoe
    • , Cody J. Wrasman
    • , Andrew A. Herzing
    • , Adam S. Hoffman
    • , Aditya Menon
    • , Alexey Boubnov
    • , Maria Vargas
    • , Simon R. Bare
    •  & Matteo Cargnello
  • Article |

    The development of efficient and low-cost electrocatalysts for the oxygen evolution reaction is critical for improving the efficiency of water electrolysis. Here, the inactive spinel CoAl2O4 is activated via iron substitution to achieve high activity and stability for water oxidation.

    • Tianze Wu
    • , Shengnan Sun
    • , Jiajia Song
    • , Shibo Xi
    • , Yonghua Du
    • , Bo Chen
    • , Wardhana Aji Sasangka
    • , Hanbin Liao
    • , Chee Lip Gan
    • , Günther G. Scherer
    • , Lin Zeng
    • , Haijiang Wang
    • , Hui Li
    • , Alexis Grimaud
    •  & Zhichuan J. Xu
  • Article |

    C-aryl glycosides are present in many natural products and of interest in drug design, but their chemical synthesis is challenging. This work reports an efficient and diastereoselective ortho-directed C−H glycosylation of arenes and heteroarenes with glycosyl chloride using a palladium catalyst.

    • Quanquan Wang
    • , Shuang An
    • , Zhiqiang Deng
    • , Wanjun Zhu
    • , Zeyi Huang
    • , Gang He
    •  & Gong Chen
  • Article |

    Efforts to harness the cellulolytic activity of enzyme assemblies have been mainly empirical due to the lack of quantification tools. Now this work reports experimental and theoretical approaches to quantify enzyme assemblies, revealing the parameters that are important for cellulolytic activity.

    • Mason R. Smith
    • , Hui Gao
    • , Ponnandy Prabhu
    • , Luke F. Bugada
    • , Cori Roth
    • , Deepika Mutukuri
    • , Christine M. Yee
    • , Lester Lee
    • , Robert M. Ziff
    • , Jung-Kul Lee
    •  & Fei Wen
  • Article |

    The synthesis of stereodefined alkenes is challenging, and often relies on the steric bias of the substituents. Here the authors report a photoredox/nickel catalysed difunctionalization of alkynes, giving access to either E- or Z-tri-substituted alkenes, depending on the photocatalyst used.

    • Chen Zhu
    • , Huifeng Yue
    • , Bholanath Maity
    • , Iuliana Atodiresei
    • , Luigi Cavallo
    •  & Magnus Rueping
  • Article |

    The production of high-value fuels from bio-derived methanol requires improvement to become economically viable. Here, process advancements for the production of high-octane gasoline are reported, and the effects that these have on making the process competitive with market rates of fossil fuels are analysed.

    • Daniel A. Ruddy
    • , Jesse E. Hensley
    • , Connor P. Nash
    • , Eric C. D. Tan
    • , Earl Christensen
    • , Carrie A. Farberow
    • , Frederick G. Baddour
    • , Kurt M. Van Allsburg
    •  & Joshua A. Schaidle
  • Article |

    The synthesis of ethanol via CO2 hydrogenation is a challenging process, often hampered by low selectivity. This work reports a Zr12 cluster-based metal–organic framework as support for cooperative Cu(i) sites that catalyse CO2 hydrogenation to ethanol with remarkable selectivity upon promotion with caesium. Credit: Cloud background, CC0 1.0 Universal Public Domain Dedication.

    • Bing An
    • , Zhe Li
    • , Yang Song
    • , Jingzheng Zhang
    • , Lingzhen Zeng
    • , Cheng Wang
    •  & Wenbin Lin
  • Article |

    Biocompatibility plays a crucial role for the development of artificial metalloenzymes (ArMs) for therapeutic applications. This work presents an ArM with a ruthenium catalyst that is protected from physiological glutathione and accumulates in cancer cell lines for metathesis-mediated prodrug activation.

    • Shohei Eda
    • , Igor Nasibullin
    • , Kenward Vong
    • , Norio Kudo
    • , Minoru Yoshida
    • , Almira Kurbangalieva
    •  & Katsunori Tanaka
  • Article |

    The fleeting nature of transition state ensembles of protein motions has precluded their experimental observation. This work provides an atomistic insight into the rate-determining structural transition of adenylate kinase during catalysis by high-pressure NMR and molecular dynamics simulations.

    • John B. Stiller
    • , S. Jordan Kerns
    • , Marc Hoemberger
    • , Young-Jin Cho
    • , Renee Otten
    • , Michael F. Hagan
    •  & Dorothee Kern
  • Article |

    Combining enzymatic and heterogeneous catalysts is challenging due to different reaction requirements. Here, a method is presented constructing single protein–polymer nanoconjugates as nanoreactors for the in situ synthesis of enzyme–metal nanohybrids with high activity at ambient conditions.

    • Xiaoyang Li
    • , Yufei Cao
    • , Kai Luo
    • , Yunze Sun
    • , Jiarong Xiong
    • , Licheng Wang
    • , Zheng Liu
    • , Jun Li
    • , Jingyuan Ma
    • , Jun Ge
    • , Hai Xiao
    •  & Richard N. Zare
  • Article |

    The roughness factor of an electrode has been generally used to increase total rates of production, though rarely as a means to improve selectivity. Now, Jaramillo, Hahn and co-workers direct the selectivity of CO reduction to multicarbon oxygenates at low overpotentials by increasing the roughness factor of nanostructured Cu electrodes.

    • Lei Wang
    • , Stephanie Nitopi
    • , Andrew B. Wong
    • , Jonathan L. Snider
    • , Adam C. Nielander
    • , Carlos G. Morales-Guio
    • , Marat Orazov
    • , Drew C. Higgins
    • , Christopher Hahn
    •  & Thomas F. Jaramillo
  • Article |

    The active sites of metal-free carbon catalysts for the oxygen reduction reaction remain still elusive. Now, Yao, Dai and co-workers combine work-function analyses with macro/micro-electrochemical measurements on highly oriented pyrolytic graphite and conclude that pentagon defects are the main active sites for acidic oxygen reduction.

    • Yi Jia
    • , Longzhou Zhang
    • , Linzhou Zhuang
    • , Hongli Liu
    • , Xuecheng Yan
    • , Xin Wang
    • , Jiandang Liu
    • , Jiancheng Wang
    • , Yarong Zheng
    • , Zhaohui Xiao
    • , Elena Taran
    • , Jun Chen
    • , Dongjiang Yang
    • , Zhonghua Zhu
    • , Shuangyin Wang
    • , Liming Dai
    •  & Xiangdong Yao