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Article
| Open AccessLight-enabled deracemization of cyclopropanes by Al-salen photocatalysis
Irradiation of chiral Al-salen complexes with violet light demonstrates efficient deracemization of cyclopropanes, enabling reactivity and enantioselectivity to be regulated simultaneously, negating the requirement for tailored catalyst–substrate recognition motifs.
- Carina Onneken
- , Tobias Morack
- & Ryan Gilmour
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Article |
Copper-catalysed enantioconvergent alkylation of oxygen nucleophiles
The enantioconvergent alkylation of oxygen nucleophiles is achieved using α-haloamides and a readily available copper catalyst, and the reaction proceeds under mild conditions in the presence of a wide variety of functional groups.
- Caiyou Chen
- & Gregory C. Fu
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Article |
Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines
The chemoselective and enantioconvergent N-alkylation of aliphatic amines, including ammonia, is achieved using chiral tridentate anionic ligands and a copper catalyst; the method shows excellent enantioselectivity and functional-group tolerance.
- Ji-Jun Chen
- , Jia-Heng Fang
- & Xin-Yuan Liu
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Article
| Open AccessCatalytic asymmetric synthesis of cannabinoids and menthol from neral
An unsymmetric, strong and confined chiral acid, a highly fluorinated imino-imidodiphosphate, catalyses the selective conversion of neral to (1R,6S)-trans-isopiperitenol, enabling sustainable routes to menthol and cannabinoids.
- Joyce A. A. Grimm
- , Hui Zhou
- & Benjamin List
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Article |
Enantioselective transition-metal catalysis via an anion-binding approach
Chiral hydrogen-bond donors bind anions of organometallic catalysts to achieve enantiocontrol and reaction-rate enhancement through ion pairing together with other non-covalent interactions.
- John M. Ovian
- , Petra Vojáčková
- & Eric N. Jacobsen
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Article |
Enantioselective [2+2]-cycloadditions with triplet photoenzymes
Triplet photoenzymes developed through genetic encoding and directed evolution result in excited-state photocatalysts that provide a valuable approach to enantioselective photochemical synthesis.
- Ningning Sun
- , Jianjian Huang
- & Yuzhou Wu
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Article |
Screening for generality in asymmetric catalysis
The analytical workflow outlined in this study allows multiple crude reaction mixtures to be analysed simultaneously, with substantial reductions in method development and analysis time, and maximizes the chances of finding catalytic systems with broad substrate scope.
- Corin C. Wagen
- , Spencer E. McMinn
- & Eric N. Jacobsen
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Article
| Open AccessOrganocatalytic stereoselective cyanosilylation of small ketones
The development of confined organocatalysts for the enantioselective cyanosilylation of small, unbiased substrates, including 2-butanone, is shown to lead to catalysts that are as selective as enzymes, with excellent levels of control.
- Hui Zhou
- , Yu Zhou
- & Benjamin List
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Article |
Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity
In the presence of three ligands and light, two distinct copper catalysts combine to produce enantioenriched secondary amides from racemic alkyl electrophiles and primary amide nucleophiles.
- Caiyou Chen
- , Jonas C. Peters
- & Gregory C. Fu
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Article |
Intercepting fleeting cyclic allenes with asymmetric nickel catalysis
Asymmetric nickel catalysis is used to intercept transient cyclic allene intermediates to achieve stereocontrol.
- Michael M. Yamano
- , Andrew V. Kelleghan
- & Neil K. Garg
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Article |
Photoenzymatic enantioselective intermolecular radical hydroalkylation
A transformation in which an ‘ene’ reductase catalyses the visible-light-induced intermolecular radical hydroalkylation of alkenes gives carbonyl compounds with a remote stereocentre in high yield and enantioselectivity.
- Xiaoqiang Huang
- , Binju Wang
- & Huimin Zhao
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Article |
Desymmetrization of difluoromethylene groups by C–F bond activation
Enantioselective activation of a single C–F bond in a difluoromethylene group is achieved using a chiral transition metal catalyst and a fluorophilic activator.
- Trevor W. Butcher
- , Jonathan L. Yang
- & John F. Hartwig
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Article |
Site-specific allylic C–H bond functionalization with a copper-bound N-centred radical
A Cu-bound nitrogen-centred radical is used to control site-specific and enantioselective allylic C–H cyanations of molecules with synthetic and medicinal relevance, such as tri- and tetrasubstituted alkenes.
- Jiayuan Li
- , Zhihan Zhang
- & Guosheng Liu
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Letter |
Enzymatic assembly of carbon–carbon bonds via iron-catalysed sp3 C–H functionalization
Evolved iron-containing enzymes based on cytochrome P450 achieve selective intermolecular alkylation of sp3 C–H bonds through a carbene C–H insertion strategy.
- Ruijie K. Zhang
- , Kai Chen
- & Frances H. Arnold
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Letter |
Desymmetrization of cyclohexanes by site- and stereoselective C–H functionalization
Unactivated cyclohexane derivatives can be desymmetrized by site- and stereoselective C–H functionalization using carbene-insertion chemistry.
- Jiantao Fu
- , Zhi Ren
- & Huw M. L. Davies
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Letter |
Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins
Nickel-catalysed coupling of racemic alkyl electrophiles and olefins in the presence of a hydrosilane is achieved with good enantioselectivity and yield under very mild reaction conditions.
- Zhaobin Wang
- , Haolin Yin
- & Gregory C. Fu
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Letter |
Enantioselective remote meta-C–H arylation and alkylation via a chiral transient mediator
Remote, enantioselective C–H activation reactions can be achieved by relaying ortho-C–H activation to the meta position, using a chiral norbornene as the mediator.
- Hang Shi
- , Alastair N. Herron
- & Jin-Quan Yu
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Article |
Quaternary stereocentres via an enantioconvergent catalytic SN1 reaction
Cooperation between a chiral hydrogen-bond-donor catalyst and a strong Lewis-acid promoter in an SN1-type reaction mediates the formation of tertiary carbocations and enables control over enantioselectivity and product distribution.
- Alison E. Wendlandt
- , Prithvi Vangal
- & Eric N. Jacobsen
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Letter |
Site-selective and stereoselective functionalization of non-activated tertiary C–H bonds
The functionalization of specific inert C–H bonds avoids the need for functional groups in organic synthesis and here the challenges of this approach are overcome using a dirhodium catalyst that is capable of C–H bond site-selectivity.
- Kuangbiao Liao
- , Thomas C. Pickel
- & Huw M. L. Davies
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Review Article |
Exploiting non-covalent π interactions for catalyst design
Our increasing understanding of non-covalent interactions involving aromatic systems is reviewed, and the use of these insights in the design of small-molecule catalysts and enzymes is surveyed.
- Andrew J. Neel
- , Margaret J. Hilton
- & F. Dean Toste
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Letter |
Catalytic asymmetric umpolung reactions of imines
Imines conventionally act as electrophiles towards carbon nucleophiles in the synthesis of amines, but the range of amines could be much extended if the carbon atom of the imine could be rendered electron-rich to allow it to act as a nucleophile toward a carbon electrophile; such a reaction can be promoted by new phase-transfer catalysts, leading to highly efficient asymmetric reactions of imines with enals.
- Yongwei Wu
- , Lin Hu
- & Li Deng
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Review Article |
Catalytic enantioselective synthesis of quaternary carbon stereocentres
Carbon atoms to which four distinct carbon substituents are attached — quaternary carbon stereocentres — are common features of molecules found in nature; in this Review, the authors discuss catalytic enantioselective reactions that have been developed during the past decade for synthesizing organic molecules containing such carbon atoms.
- Kyle W. Quasdorf
- & Larry E. Overman
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Article |
Multifunctional organoboron compounds for scalable natural product synthesis
A catalytic process is reported that begins with a highly selective copper–boron addition to a monosubstituted allene, and in which the resulting boron-substituted organocopper intermediate then participates in a chemoselective, site-selective and enantioselective allylic substitution; this approach is used in the enantioselective synthesis of gram quantities of two natural products.
- Fanke Meng
- , Kevin P. McGrath
- & Amir H. Hoveyda
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Letter |
Simple organic molecules as catalysts for enantioselective synthesis of amines and alcohols
A set of small organic molecules catalyse reactions of unsaturated organoboron reagents with imines and carbonyls to produce amines and alcohols in high enantiomeric purity efficiently, speedily and at low cost through sustainable protocols.
- Daniel L. Silverio
- , Sebastian Torker
- & Amir H. Hoveyda
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Letter |
Asymmetric spiroacetalization catalysed by confined Brønsted acids
Spiroacetals are found in a broad range of biologically active compounds, including small insect pheromones and more complex macrocycles; a confined imidodiphosphoric-acid catalyst is now reported that is able to facilitate the stereoselective synthesis of small, unfunctionalized spiroacetals.
- Ilija Čorić
- & Benjamin List
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Letter |
Free-standing mesoporous silica films with tunable chiral nematic structures
Some beetle shells exhibit iridescence owing to the chiral organization of chitin making up the beetle's exoskeleton. Inspired by this, these authors fabricate thin glass films with helical pores introduced using a renewable cellulose template. The chiral structure allows the material, which can be free-standing, to selectively reflect light at a specific wavelength that can be tuned across the visible spectrum by altering the ratio of silica to cellulose during synthesis.
- Kevin E. Shopsowitz
- , Hao Qi
- & Mark J. MacLachlan
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Research Highlights |
Organic chemistry: Catalysts cooperate