Catalysis articles within Nature Chemistry

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  • News & Views |

    Although light-driven conversion of carbon dioxide receives widespread attention, it is also criticized due to the challenge of discerning true product formation from that of impurities. Now, significantly advanced guidelines for proper product identification have been developed, so we can better trust in what we see.

    • Jennifer Strunk

  • Article |

    The design and improvement of enzymes based on physical principles remain challenging. Now, the vibrational Stark effect has been used to demonstrate how an electrostatic model can unify the catalytic effects of distinct chemical forces in a quantitative manner and guide the design of enzyme variants that outperform their natural counterpart.

    • Chu Zheng
    • , Zhe Ji
    •  & Steven G. Boxer

  • Article |

    Although Li–O2 batteries offer high theoretical capacities, redox mediators are necessary to control intermediate reaction kinetics and to limit electrode passivation. Now it has been shown that a family of triarylmethyl cations can rival top-performing quinone-based redox mediators. Cations with sluggish catalytic rates were found to suppress surface-mediated O2 reduction and achieve higher capacitances.

    • Erik J. Askins
    • , Marija R. Zoric
    •  & Ksenija D. Glusac

  • Article
    | Open Access

    An enzymatic reaction installs endogenous β-amino acids in proteins with unique reactivity. Now it has been shows that this reaction can be used for site-specific modification with tetrazine dienophiles to introduce labels onto target proteins. Applications include generation of a radiolabel chelator-modified Her2-binding Affibody and intracellular, fluorescently labelled cell division protein FtsZ.

    • Daniel Richter
    • , Edgars Lakis
    •  & Jörn Piel

  • News & Views |

    Lactams and pyridines are privileged scaffolds, but strategies for combining these groups into one molecule are lacking. Now, N–N pyridinium ylides have been shown to form triplet state diradicals under photoinduced energy transfer, and subsequent [3+2] cycloaddition with the tethered alkene enables the synthesis of diverse ortho-pyridyl lactams.

    • Peng-Zi Wang
    •  & Jia-Rong Chen

  • Article |

    There is currently a lack of effective synthetic strategies for combining lactams and pyridines within a single molecular structure. Now, diastereoselective pyridyl lactamization has been developed using a photoinduced [3+2] cycloaddition of triplet diradical N–N pyridinium ylides with pendant alkenes. This method provides a useful synthon for preparing pyridyl γ- and δ-lactam scaffolds with syn-configuration.

    • Wooseok Lee
    • , Yejin Koo
    •  & Sungwoo Hong

  • Article |

    Stabilization of RNAs for storage, transport and biological application remains a profound challenge. Now, it has been shown that reversible 2′-OH acylation with easily accessible acylimidazoles unlocks efficient protection of RNA. RNA can be deprotected by non-basic nucleophiles or spontaneously in cells to restore RNA functions.

    • Linglan Fang
    • , Lu Xiao
    •  & Eric T. Kool

  • Article |

    Although several transition-metal carbene complexes have been isolated and used for catalytic carbene transfer reactions, few metal difluorocarbene complexes have been reported. Now, the synthesis, characterization and reactivity of isolable copper(I) difluorocarbene complexes has been reported, which has enabled the development of a copper-catalysed difluorocarbene transfer reaction to access fluorinated compounds from simple chemical feedstocks.

    • Xin Zeng
    • , Yao Li
    •  & Xingang Zhang

  • News & Views |

    The atomically precise assembly of metal nanoparticles offers vast possibilities for materials chemistry. Ring-shaped polyoxometalates have now served to stabilize Ag30 nanoparticles with exposed surfaces.

    • Carsten Streb

  • Article
    | Open Access

    The use of main-group elements in radical cross-coupling reactions has been little explored. Now, a low-valency bismuth complex has been shown to emulate the behaviour of first-row transition metals and undergo single-electron-transfer oxidative addition to redox-active electrophiles, leading to the development of a bismuth-catalysed C–N coupling reaction between amines and carboxylic acids.

    • Mauro Mato
    • , Davide Spinnato
    •  & Josep Cornella

  • Article |

    The diverse site-selective functionalization, including multi-functionalization, of C=C double bonds and C(sp3)–H bonds remains a largely unmet challenge. Now, a palladium-catalysed aerobic oxidative method has been developed for the multi-site programmable functionalization of terminal olefins via a strategy that controls the reaction sequence between alkene isomerization and oxidative functionalization.

    • Zhengxing Wu
    • , Jingjie Meng
    •  & Wanbin Zhang

  • Article
    | Open Access

    Catalytic enantioselective approaches to access chiral organophosphorus compounds are rare. A two-stage catalytic strategy for the synthesis of diverse enantioenriched P(V) compounds has now been developed: a bifunctional iminophosphorane superbase enables enantioselective nucleophilic desymmetrization, followed by downstream enantiospecific diversification of the resulting intermediate by substitution with medicinally relevant O-, N- and S-based nucleophiles.

    • Michele Formica
    • , Tatiana Rogova
    •  & Darren J. Dixon

  • Article |

    Functionalization of unsymmetrical internal alkenes usually takes place with low regioselectivity, giving a mixture of isomers. Now, a highly regio- and enantioselective remote 1,n-dioxygenation of internal alkenes using a palladium catalyst has been developed for the synthesis of chiral 1,n-diols. Regioselectivity tuning was demonstrated by altering the rate-determining step, enabled by the phenyl-substituted Pyox ligand.

    • Xiaonan Li
    • , Tilong Yang
    •  & Guosheng Liu

  • Article |

    Methods for the direct construction of 1,3-disubstituted planar chiral ferrocenes are elusive. Now, a modular platform enables the construction of planar chirality in 1,3-disubstituted ferrocenes/ruthenocenes via enantioselective relay remote C–H arylation. The strategy involves an initial enantiodetermining ortho-C‒H activation enabled by a Pd(II)/chiral amino-acid ligand, followed by relay to the remote meta-position by a bridgehead-substituted norbornene mediator.

    • Lan Zhou
    • , Hong-Gang Cheng
    •  & Qianghui Zhou

  • News & Views |

    Enantioenriched β-amino acid derivatives are attractive synthetic targets, considering the significance of these motifs in medicinal and material chemistry. Now, using ambiphilic ynamides as two-carbon synthons in a four-component reaction, three classes of β-amino amides with well-defined stereocentres can be accessed.

    • Sunliang Cui
    •  & Linwei Zeng

  • Article |

    β-Amino acids are broadly found in biomimetic drugs and therapeutics, but the general synthesis of chiral β-amino amides remains limited. An organocatalytic four-component reaction has now been developed for their asymmetric synthesis with notable efficiency, chemoselectivity and stereoselectivity. This protocol shows broad product scope and provides a shortcut to other important structures.

    • Jun Wei
    • , Jian Zhang
    •  & Bin Tan

  • Article |

    Polyhydroxyalkanoates are potential substitutes for non-degradable polyolefin plastics. Now, it has been shown that structurally related methylated polyhydroxybutyrates, synthesized from carbon monoxide and 2-butenes, can provide a full suite of polyolefin-like polymers. These materials can be recycled or upcycled, and their properties can be easily tuned by varying the cis/trans ratio of the starting materials.

    • Zhiyao Zhou
    • , Anne M. LaPointe
    •  & Geoffrey W. Coates

  • Article
    | Open Access

    A simple and general enantioselective method for the synthesis of non-fused lower carbo[n]helicenes (n = 4–6) is reported. The helicene scaffold is constructed with high enantioselectivity by Pd0-catalysed C–H arylation with aryl bromides. A bifunctional ligand provides a precise chiral environment that allows fine control of the enantioselectivity.

    • Shu-Min Guo
    • , Soohee Huh
    •  & Olivier Baudoin

  • News & Views |

    Plasmonic heating by nanoparticles has been used to promote a range of chemical reactions. Now, thermoplasmonic activation has been applied to latent ruthenium catalysts, enabling olefin metathesis initiated by visible and infrared light.

    • Leah N. Appelhans

  • Article |

    Borylated bicyclopentanes and bicyclohexanes are valuable compounds in drug research but are difficult to prepare. Now, an iridium-catalysed method has been developed for the borylation of the bridgehead tertiary C–H bonds in bicyclopentanes and bicyclohexanes, providing access to a variety of highly decorated bicyclic cores.

    • Isaac F. Yu
    • , Jenna L. Manske
    •  & John F. Hartwig

  • Article |

    Photochemical reduction of CO2 is a significant challenge and many existing methods use catalysts containing rare metals. Now a metal-free version of this reaction—with high selectivity for formate generation over H2 or CO—has been achieved that features a combination of carbazole photosensitizer and organohydride catalyst.

    • Weibin Xie
    • , Jiasheng Xu
    •  & Ryosuke Matsubara

  • News & Views |

    2+2-cycloaddition reactions have long been considered key transformations in the biosynthesis of cyclobutane-containing natural products, but enzymes for these reactions have not yet been identified. Now, a 2+2 cyclase has been discovered, characterized and bioengineered to catalyse cycloadditions with different selectivity.

    • Bo Zhang
    •  & Hui Ming Ge

  • News & Views |

    The selective removal of one oxygen atom from sulfones, without over-reduction to sulfide, is a challenging task. Now, through organocatalysis and incorporation of a cyano group into the sulfone, an asymmetric deoxygenation strategy has been developed, providing an efficient method for the synthesis of chiral sulfinyl compounds.

    • Elżbieta Wojaczyńska
    •  & Jacek Wojaczyński

  • Article |

    The direct conversion of sulfones to chiral sulfinyl compounds is one of the major challenges in the fields of asymmetric synthesis and organosulfur chemistry. Now, through incorporation of a cyano group into the sulfone, an organocatalytic asymmetric deoxygenation strategy has been developed that enables the synthesis of chiral sulfinyl compounds.

    • Shengli Huang
    • , Zhen Zeng
    •  & Hailong Yan

  • Article |

    Controlling various selectivities in radical reactions presents both formidable challenges and great opportunities. Now, Co(II)-based metalloradical catalysis has enabled the concurrent control of multiple convergences and selectivities in intermolecular radical allylic C−H amination. The reaction provides access to valuable chiral α-tertiary amines directly from an isomeric mixture of alkenes.

    • Pan Xu
    • , Jingjing Xie
    •  & X. Peter Zhang

  • Article
    | Open Access

    Asymmetric systems for catalytic carbohydrate functionalization are mostly limited to chiral copper complexes and organocatalysts. Now, a synergistic chiral Rh(I)- and organoboron-catalysed site-selective functionalization of carbohydrate polyols has been developed, giving stereocontrolled access to biologically relevant arylhydronaphthalene glycosides. Enantio-, diastereo-, regio- and anomeric control and dynamic kinetic resolution were found to be concomitantly operative.

    • V. U. Bhaskara Rao
    • , Caiming Wang
    •  & Charles C. J. Loh

  • Article |

    Heteroatom–heteroatom cross-couplings have so far remained elusive. Now, a copper-catalysed enantioselective S–O cross-coupling of diverse diols or triols with sulfonyl chlorides has been realized via a single-electron reductive elimination manifold. The reaction provides access to value-added chiral C3 building blocks and inositol phosphates through enantioselective desymmetrization of biomass-derived alcohols.

    • Yong-Feng Cheng
    • , Zhang-Long Yu
    •  & Xin-Yuan Liu

  • News & Views |

    Radical-mediated functionalization streamlines access to complex synthetic targets. Now, a sulfonium-based donor–acceptor pair enables photoinduced charge-transfer interactions to access electronically diverse aryl radicals. Reaction with enol ethers or isocyanide provides a metal-free method for arene functionalization.

    • Taylor N. Bednar
    •  & David A. Nagib

  • Article |

    The nitrogen reduction reaction is an extremely valuable but energy-intensive process. Now, a coordination polymer based on a [Zn–N2–Zn] unit has been shown to promote the formation of ammonia under ambient conditions by a photocatalytic reaction. The N2 moieties within the framework are reduced, creating unsaturated [Zn2+···Zn+] intermediates that are able to capture external N2 and sustain the cycle.

    • Yan Xiong
    • , Bang Li
    •  & Zhong Jin

  • Article |

    The strong regiochemical preferences of electrophilic aromatic substitution have played a key role in defining the diversity of accessible chemical space. Now, it has been shown that the electrophilic arylation of phenols can be achieved at the electronically disfavoured meta-position via a formal 1,2-migration of a key σ-complex intermediate.

    • Aaron Senior
    • , Katie Ruffell
    •  & Liam T. Ball

  • Article |

    Direct oxidative methods for the enantioselective synthesis of heterobiaryl compounds that exhibit axial chirality remain elusive. Now, the use of an iron catalyst in the presence of a chiral PyBOX ligand and an oxidant enables the direct coupling of naphthols and indoles with high levels of enantio- and cross-selectivity.

    • Richard R. Surgenor
    • , Xiangqian Liu
    •  & Martin D. Smith

  • Article |

    Photoactivation of EDA complexes was previously limited to electronically biased partners to secure productive charge-transfer interactions. Now, the participation of triarylsulfonium salts—formed by selective C–H sulfenylation—in photoactive EDA complexes with catalytic triarylamine donors provides a site-selective and metal-free strategy for the generation of aryl radicals and the formal C–H functionalization of native arenes.

    • Abhishek Dewanji
    • , Leendert van Dalsen
    •  & David J. Procter

  • Review Article |

    The light-driven conversion of abundant resources such as CO2 and H2O into chemical fuels for energy storage is crucial to end our dependence on fossil fuels. This Review highlights how molecular catalysts and photosensitizers can be grafted onto metal–organic frameworks to combine the advantages of both classes of compounds. Different synthetic strategies are discussed, along with their advantages and limitations.

    • P. M. Stanley
    • , J. Haimerl
    •  & J. Warnan

  • Article |

    The synthesis of cyclic polymers remains challenging. Now a trifunctional B-P-B frustrated Lewis pair has been shown to enable easy access to cyclic acrylic polymers through a bimolecular mechanism. These cyclic polymers have enhanced thermodynamic properties compared with their linear counterparts, while maintaining high chemical recyclability.

    • Yanjiao Song
    • , Jianghua He
    •  & Eugene Y.-X. Chen

  • Article |

    Expanding the biocatalysis toolbox for C–N bond formation is of great value. Now, a biocatalytic amination strategy using a new-to-nature mechanism involving nitrogen-centred radicals has been developed. The transformations are enabled by synergistic photoenzymatic catalysis, providing intra- and intermolecular hydroamination products with high yields and levels of enantioselectivity.

    • Yuxuan Ye
    • , Jingzhe Cao
    •  & Todd K. Hyster

  • Article |

    Methods to access organofluorine compounds with a trifluoromethyl- and fluoro-substituted carbon stereogenic centre are severely limited. Now, a flexible and stereodivergent approach has been developed for the efficient preparation of homoallylic alcohols containing this moiety. Conversion to polyfluoro furanosides and pyranosides has been demonstrated, which is relevant to antiviral drug development.

    • Shibo Xu
    • , Juan del Pozo
    •  & Amir H. Hoveyda

  • Article |

    The facile release of corrosive HCl gas and plasticizers from poly(vinyl chloride) (PVC) makes it a challenging material to recycle. Now, it has been shown that PVC waste can be directly used as a halogen source to synthesize chloroarenes. This paired electro(de)chlorination is mediated by a phthalate plasticizer already contained in PVC waste.

    • Danielle E. Fagnani
    • , Dukhan Kim
    •  & Anne J. McNeil

  • Article |

    Kinetic isotope effect studies can provide valuable insights into the complex mechanisms of the oxygen reduction reaction; however, inaccessibility to ultra-high-purity D2O has made this difficult. Now, a methodology to prepare ultra-pure D2O has been developed and inverse kinetic isotope effects have subsequently been measured for the oxygen reduction reaction on platinum single-crystal surfaces, providing mechanistic insights.

    • Yao Yang
    • , Rishi G. Agarwal
    •  & Héctor D. Abruña

  • News & Views |

    The direct carbon isotope exchange reaction on α-amino acids is highly desirable, as existing labelling methods require several synthetic steps and harsh conditions. Now, an aldehyde-catalysed carboxylate exchange with isotopically labelled *CO2 has enabled the direct formation of 11C, 13C and 14C-labelled α-amino acids.

    • Karoline T. Neumann
    •  & Troels Skrydstrup

  • Article |

    Carbon-labelled α-amino acids are valuable compounds in drug development and nuclear medicine, but are difficult and time consuming to prepare. Now, an aldehyde-catalysed method has been developed for the direct C1-labelling of α-amino acids using *CO2 (* = 14, 13, 11), providing access to many proteinogenic and non-natural labelled α-amino acids.

    • Odey Bsharat
    • , Michael G. J. Doyle
    •  & Rylan J. Lundgren

  • Article
    | Open Access

    The circadian rhythm generates out-of-equilibrium metabolite oscillations controlled by feedback loops under light/dark cycles. Now, it has been shown that these life-like properties can emerge from a non-equilibrium nanosystem comprising a binary population of enzyme-containing polymersomes capable of light-gated chemical communication, controllable feedback and coupling to macroscopic oscillations.

    • Omar Rifaie-Graham
    • , Jonathan Yeow
    •  & Molly M. Stevens

  • Article
    | Open Access

    The rapid assembly of complex scaffolds in a single step from simple precursors would be an ideal reaction in terms of efficiency and sustainability. Now, the single-step construction of alkaloid-like frameworks from three dynamically assembled precursors has been reported. Using a dual-catalytic system, the transformation involves a hydride shuttle process initiated by a hydride donation event.

    • Immo Klose
    • , Giovanni Di Mauro
    •  & Nuno Maulide

  • Article |

    Technologies for profiling biological environments with high spatiotemporal resolution are in demand to enable the discovery of new targets for addressing unmet clinical needs. Now, a deep red light-mediated photocatalytic strategy for the targeted activation of aryl azides has been developed. This platform enables mapping of protein microenvironments in physiologically relevant systems.

    • Nicholas Eng Soon Tay
    • , Keun Ah Ryu
    •  & Tomislav Rovis

  • News & Views |

    Noyori-type catalysts and inorganic bases are frequently used together for homogeneous hydrogenation, but key intermediates have not yet been isolated. Now, the structure and reactivity of a long-postulated intermediate — the alkali metal amidate complex — have been reported through experimental and computational studies.

    • Pavel A. Dub

  • Article |

    Noyori-type hydrogenation catalysts consist of an N–H moiety coordinated to a metal centre. Now, a metal-hydride amidate complex (HMn–NLi) has been isolated and found to have superior reactivity and catalytic performance compared with the corresponding HMn–NH complex, highlighting the superiority of M/NM′ bifunctional catalysis over the classic M/NH bifunctional catalysis for hydrogenation reactions.

    • Yujie Wang
    • , Shihan Liu
    •  & Qiang Liu

  • Article |

    Cyclic polymers are topologically interesting and envisioned as a lubricant material, but methods for the scalable synthesis of pure cyclic polymers are currently elusive. Now, a scalable process has been developed by leveraging heterogeneity of the catalysts with the help of compartmentalized custom glassware, namely, a cyclic polymer dispenser.

    • Ki-Young Yoon
    • , Jinkyung Noh
    •  & Robert H. Grubbs

  • Article |

    Given the importance of amine compounds, methods for their synthesis continue to be in high demand. Now, a palladium-catalysed strategy has been developed for the selective oxidative amination of unactivated olefins with Lewis basic amines, via C(sp3)–H activation, forming architecturally versatile and functionally diverse allylamines in a single step.

    • Yangbin Jin
    • , Yaru Jing
    •  & Huanfeng Jiang

  • In Your Element |

    Lukas Veth and Paweł Dydio discuss the importance of ligands in transition metal catalysis, looking at the success story of xantphos and why it should earn the title of ‘privileged ligand’.

    • Lukas Veth
    •  & Paweł Dydio

  • News & Views |

    An alcohol-functionalized cyclophane has been shown to form a bowl-shaped cavity large enough to host tris(bipyridine)ruthenium(ii). The macrocycle captures, and suppresses the activity of, the ruthenium complex in water but, when oxidized to its ketone-bearing counterpart, releases the ruthenium guest.

    • David Van Craen

  • News & Views |

    Supramolecular catalysis can emulate many features of enzymatic transformations. Now, a complex proton wire mechanism — enabling the dual activation of a nucleophile and an electrophile through reciprocal proton transfer — has been shown to operate during the β-glycosylation of sugars within a self-assembled capsule.

    • Cally J. E. Haynes
    •  & Larissa K. S. von Krbek

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