Featured
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Synthesis of non-canonical amino acids through dehydrogenative tailoring
- Xin Gu
- , Yu-An Zhang
- & Alison E. Wendlandt
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Article |
Unlocking carbene reactivity by metallaphotoredox α-elimination
Metal carbenes are accessed using a metallaphotoredox platform that exploits iron carbene reactivity using readily available chemical feedstocks and α-elimination.
- Benjamin T. Boyle
- , Nathan W. Dow
- & David W. C. MacMillan
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| Open AccessPhotocatalytic doping of organic semiconductors
A previously undescribed photocatalytic approach enables the effective p-type and n-type doping of organic semiconductors at room temperature using only widely available weak dopants such as oxygen and triethylamine.
- Wenlong Jin
- , Chi-Yuan Yang
- & Simone Fabiano
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Article |
Couple-close construction of polycyclic rings from diradicals
A couple-close approach used to build semisaturated ring systems from dual radical precursors allows sampling of regions of underexplored chemical space, leading to an annulation that can be used for late-stage functionalization of pharmaceutical scaffolds.
- Alice Long
- , Christian J. Oswood
- & David W. C. MacMillan
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Alkene dialkylation by triple radical sorting
We use bimolecular homolytic substitution catalysis to sort an electrophilic radical and a nucleophilic radical across an unactivated alkene, accelerating access to pharmaceutically relevant C(sp3)-rich molecules and defining a mechanistic approach for alkene dialkylation.
- Johnny Z. Wang
- , William L. Lyon
- & David W. C. MacMillan
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Article
| Open AccessPhotocatalytic phosphine-mediated water activation for radical hydrogenation
Using a photocatalytic phosphine-mediated radical process under mild conditions enables direct hydrogen atom transfer to closed-shell π systems for activation of water.
- Jingjing Zhang
- , Christian Mück-Lichtenfeld
- & Armido Studer
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Article |
General cross-coupling reactions with adaptive dynamic homogeneous catalysis
A self-adjustive catalytic system with nickel under visible-light-driven redox reaction conditions provides a general method for carbon–(hetero)atom cross-coupling reactions and is demonstrated for nine different bond-forming reactions.
- Indrajit Ghosh
- , Nikita Shlapakov
- & Burkhard König
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Article |
General access to cubanes as benzene bioisosteres
The synthesis of 1,3- and 1,2-disubstituted cubanes is achieved using a cyclobutadiene precursor and a photolytic carboxylation reaction, respectively, and copper-catalysed amination, arylation, alkylation and trifluoromethylation reactions have been developed enabling the use of cubanes as bioisosteres of benzenes in drug design.
- Mario P. Wiesenfeldt
- , James A. Rossi-Ashton
- & David W. C. MacMillan
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Article |
Solar-to-hydrogen efficiency of more than 9% in photocatalytic water splitting
Photocatalytic water splitting with a high solar-to-hydrogen efficiency of more than nine per cent is achieved using pure water, concentrated solar light and an indium gallium nitride photocatalyst.
- Peng Zhou
- , Ishtiaque Ahmed Navid
- & Zetian Mi
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Electrophotocatalytic oxygenation of multiple adjacent C–H bonds
Installation of multiple C–O bonds by concurrent oxygenation of contiguous C–H bonds in a selective fashion is highly desirable, and this is achieved by repeated operation of a potent oxidative catalyst via electrophotocatalysis.
- Tao Shen
- , Yi-Lun Li
- & Tristan H. Lambert
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Spatiotemporal imaging of charge transfer in photocatalyst particles
Photovoltage measurements on cuprous oxide photocatalyst particles are used to spatiotemporally track the charge transfer processes on the femtosecond to second timescale at the single-particle level.
- Ruotian Chen
- , Zefeng Ren
- & Can Li
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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 |
Photoexcited nitroarenes for the oxidative cleavage of alkenes
Oxidative cleavage of alkenes is achieved using nitroarenes and light irradiation as an alternative to using ozone to break the carbon–carbon bonds, avoiding the explosive intermediates formed with ozone.
- Alessandro Ruffoni
- , Charlotte Hampton
- & Daniele Leonori
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Floating perovskite-BiVO4 devices for scalable solar fuel production
This work introduces lightweight, leaf-like photoelectrochemical devices for unassisted water splitting and syngas production, which could be used in the fabrication of floating systems for solar fuel production.
- Virgil Andrei
- , Geani M. Ucoski
- & Erwin Reisner
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An asymmetric sp3–sp3 cross-electrophile coupling using ‘ene’-reductases
A highly chemoselective and enantioselective cross-electrophile coupling using ‘ene’-reductases is reported, and photoexcited enzymes demonstrate the ability to carry out reactions between electrophiles that are not known for small-molecule catalysis.
- Haigen Fu
- , Jingzhe Cao
- & Todd K. Hyster
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Article
| Open AccessReconstructed covalent organic frameworks
A protocol in which monomers are pre-organized using a reversible and removable urea linkage enables the production of covalent organic frameworks with higher crystallinity and porosity than those produced using standard approaches with randomly aligned monomers.
- Weiwei Zhang
- , Linjiang Chen
- & Andrew I. Cooper
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Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer
A strain-release approach, realized by visible-light-mediated triplet energy transfer catalysis, enabled an intermolecular [2π+2σ]-photocycloaddition.
- Roman Kleinmans
- , Tobias Pinkert
- & Frank Glorius
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Article |
Metallaphotoredox-enabled deoxygenative arylation of alcohols
A metallaphotoredox-based cross-coupling platform is capable of activating a wide range of free alcohols using N-heterocyclic carbene salts, cleaving C–O bonds to form free carbon radicals that are then used to form new C–C bonds.
- Zhe Dong
- & David W. C. MacMillan
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Photocatalytic solar hydrogen production from water on a 100-m2 scale
Carbon-neutral hydrogen can be produced through photocatalytic water splitting, as demonstrated here with a 100-m2 array of panel reactors that reaches a maximum conversion efficiency of 0.76%.
- Hiroshi Nishiyama
- , Taro Yamada
- & Kazunari Domen
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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 |
CO2 doping of organic interlayers for perovskite solar cells
CO2 and ultraviolet light are used to initiate the p-type doping of spiro-OMeTAD:LiTFSI films, which show enhanced efficiencies when used as hole-transporting layers in solar cells and have shorter fabrication times compared with interlayers doped using conventional methods.
- Jaemin Kong
- , Yongwoo Shin
- & André D. Taylor
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Article |
A radical approach for the selective C–H borylation of azines
Selective borylation of azines—nitrogen-containing aromatic heterocycles used in the synthesis of many pharmaceuticals—is made possible by forming a radical from an aminoborane using a photocatalyst.
- Ji Hye Kim
- , Timothée Constantin
- & Daniele Leonori
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Article |
Metallaphotoredox aryl and alkyl radiomethylation for PET ligand discovery
A versatile and rapid metallaphotoredox catalytic method of making 3H- and 11C-labelled tracer compounds for use in positron emission tomography (PET) is reported.
- Robert W. Pipal
- , Kenneth T. Stout
- & David W. C. MacMillan
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Article |
Metal-free photoinduced C(sp3)–H borylation of alkanes
Metal-free borylation of C(sp3)–H bonds by violet-light-induced hydrogen atom transfer is reported, demonstrating high selectivity for the substitution of methyl C–H bonds over other weaker C–H bonds.
- Chao Shu
- , Adam Noble
- & Varinder K. Aggarwal
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Article |
Light-driven post-translational installation of reactive protein side chains
A wide range of side chains are installed into proteins by addition of photogenerated alkyl or difluroalkyl radicals, providing access to new functionality and reactivity in proteins.
- Brian Josephson
- , Charlie Fehl
- & Benjamin G. Davis
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Article |
Filling metal–organic framework mesopores with TiO2 for CO2 photoreduction
Investigation of a chromium-based metal–organic framework shows that the location of added TiO2 inside specific mesopores strongly affects the ability of the material to catalyse photoreduction of CO2.
- Zhuo Jiang
- , Xiaohui Xu
- & Hexiang Deng
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A photochemical dehydrogenative strategy for aniline synthesis
A dual cobalt and photocatalysis system provides a way to assemble anilines from cyclohexanones and amines by progressively dehydrating the intermediate imine.
- Shashikant U. Dighe
- , Fabio Juliá
- & Daniele Leonori
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Photocatalytic water splitting with a quantum efficiency of almost unity
Water splitting with an internal quantum efficiency of almost unity is achieved using a modified semiconductor photocatalyst that selectively promotes the hydrogen and oxygen evolution reactions on separate crystal facets.
- Tsuyoshi Takata
- , Junzhe Jiang
- & Kazunari Domen
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Article |
Discovery and characterization of an acridine radical photoreductant
Photoexcited acridine radical catalysts are found to have redox potentials more reducing than lithium, which is attributed to the population of higher-energy doublet excited states via a twisted intramolecular charge-transfer species.
- Ian A. MacKenzie
- , Leifeng Wang
- & David A. Nicewicz
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Article |
Copper-mediated synthesis of drug-like bicyclopentanes
A one-step, three-component radical coupling of [1.1.1]propellane by a photoredox reaction mediated by a copper catalyst produces drug-like bicyclopentanes.
- Xiaheng Zhang
- , Russell T. Smith
- & David W. C. MacMillan
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Letter |
Photoredox catalysis using infrared light via triplet fusion upconversion
Photoredox transformations are achieved with infrared light by using triplet fusion upconversion that converts infrared into visible light, enabling the use of photoredox chemistry on larger scales and through barriers that are impenetrable by visible light.
- Benjamin D. Ravetz
- , Andrew B. Pun
- & Luis M. Campos
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Letter |
Catalytic deracemization of chiral allenes by sensitized excitation with visible light
Photochemical deracemization through irradiation with visible light in the presence of a chiral sensitizer enables the direct formation of single enantiomers from a racemic mixture of the same compound.
- Alena Hölzl-Hobmeier
- , Andreas Bauer
- & Thorsten Bach
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Letter |
A protein functionalization platform based on selective reactions at methionine residues
This methionine-selective functionalization strategy uses hypervalent iodine reagents to introduce new groups via the formation of a sulfonium intermediate, which can then undergo further visible-light-mediated reactions to form a diverse range of protein conjugates.
- Michael T. Taylor
- , Jennifer E. Nelson
- & Matthew J. Gaunt
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Letter |
Multicomponent synthesis of tertiary alkylamines by photocatalytic olefin-hydroaminoalkylation
Complex tertiary alkylamines are prepared in one step from readily available amines, carbonyls and alkenes, via the visible-light-mediated reduction of in-situ-generated iminium ions to form alkyl-substituted α-amino radicals.
- Aaron Trowbridge
- , Dominik Reich
- & Matthew J. Gaunt
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Letter |
Cooperative asymmetric reactions combining photocatalysis and enzymatic catalysis
A cooperative chemoenzymatic reaction combines photocatalytic alkene isomerization with enzymatic reduction to generate enantioenriched products in a stereoconvergent manner.
- Zachary C. Litman
- , Yajie Wang
- & John F. Hartwig
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Letter |
Direct arylation of strong aliphatic C–H bonds
Direct coupling of aliphatic C–H nucleophiles to aryl electrophiles is described, through the combination of light-driven polyoxometalate hydrogen atom transfer and nickel catalysis.
- Ian B. Perry
- , Thomas F. Brewer
- & David W. C. MacMillan
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Letter |
Decarboxylative sp3 C–N coupling via dual copper and photoredox catalysis
The synergistic combination of copper catalysis and photoredox catalysis forms sp3 C–N bonds in a rapid, room-temperature coupling protocol with high efficiencies and regioselectivities and a broad substrate scope.
- Yufan Liang
- , Xiaheng Zhang
- & David W. C. MacMillan
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Letter |
Generating carbyne equivalents with photoredox catalysis
A photocatalytic strategy is described that generates diazomethyl radicals as direct equivalents of carbynes, which are often too reactive to use, enabling the functionalization of a range of medically useful compounds.
- Zhaofeng Wang
- , Ana G. Herraiz
- & Marcos G. Suero
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Review Article |
Enhancing the potential of enantioselective organocatalysis with light
This Review discusses recent developments in the combination of organocatalysis and photochemistry for the activation of molecules, which has enabled previously inaccessible reaction pathways and influenced many fields of chemical research.
- Mattia Silvi
- & Paolo Melchiorre
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Letter |
Visible-light-driven methane formation from CO2 with a molecular iron catalyst
An iron tetraphenylporphyrin complex is shown to catalyse the reduction of carbon dioxide to methane upon visible light irradiation at ambient temperature and pressure.
- Heng Rao
- , Luciana C. Schmidt
- & Marc Robert
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Letter |
Selective sp3 C–H alkylation via polarity-match-based cross-coupling
Using a triple catalytic approach, a selective sp3 C–H alkylation is demonstrated that is applicable in late-stage functionalization of pharmaceutical compounds.
- Chip Le
- , Yufan Liang
- & David W. C. MacMillan
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Letter |
Amide-directed photoredox-catalysed C–C bond formation at unactivated sp3 C–H bonds
The formation of carbon–carbon bonds is achieved via directed cleavage of traditionally non-reactive carbon–hydrogen bonds and their subsequent coupling with readily available alkenes.
- John C. K. Chu
- & Tomislav Rovis
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Letter |
Catalytic alkylation of remote C–H bonds enabled by proton-coupled electron transfer
Catalytic alkylation of C–H bonds is achieved via homolysis of N–H bonds of N-alkyl amides through proton-coupled electron transfer.
- Gilbert J. Choi
- , Qilei Zhu
- & Robert R. Knowles
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Letter |
Metallaphotoredox-catalysed sp3–sp3 cross-coupling of carboxylic acids with alkyl halides
The long-sought direct formation of a bond between two sp3-hybridized carbon atoms is achieved by the merger of photoredox and nickel catalysis using only simple carboxylic acids and alkyl halides as starting materials.
- Craig P. Johnston
- , Russell T. Smith
- & David W. C. MacMillan
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Letter |
Asymmetric catalytic formation of quaternary carbons by iminium ion trapping of radicals
A combination of photoredox and asymmetric organic catalysis enables enantioselective radical conjugate additions to β,β-disubstituted cyclic enones to construct quaternary carbon stereocentres with high fidelity.
- John J. Murphy
- , David Bastida
- & Paolo Melchiorre
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Letter |
Sub-particle reaction and photocurrent mapping to optimize catalyst-modified photoanodes
Using single-molecule fluorescence imaging of photoelectrocatalysis, the charge-carrier activities on single TiO2 nanorods and the corresponding water-oxidation photocurrent are mapped at high spatiotemporal resolution, revealing the best catalytic sites and the most effective sites for depositing an oxygen evolution catalyst.
- Justin B. Sambur
- , Tai-Yen Chen
- & Peng Chen
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Letter |
Alcohols as alkylating agents in heteroarene C–H functionalization
The biochemical process of spin-centre shift is used to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors; this represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis.
- Jian Jin
- & David W. C. MacMillan
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Letter |
Switching on elusive organometallic mechanisms with photoredox catalysis
Despite advances in carbon–carbon fragment couplings, the ability to forge carbon–oxygen bonds in a general fashion via nickel catalysis has been largely unsuccessful; here, visible-light-excited photoredox catalysts are shown to provide transient access to Ni(iii) species that readily participate in reductive elimination, leading to carbon–oxygen coupling.
- Jack A. Terrett
- , James D. Cuthbertson
- & David W. C. MacMillan
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Letter |
Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution
Mapping the frontier-orbital interactions with atom specificity using X-ray laser-based femtosecond-resolution spectroscopy reveals that spin crossover and ligation determine the sub-picosecond excited-state dynamics of a transition-metal complex in solution.
- Ph. Wernet
- , K. Kunnus
- & A. Föhlisch