Photoinduced cerium-catalyzed C-H acylation of unactivated alkanes

Article Chemistry, Multidisciplinary

Photoinduced Acylations Via Azolium-Promoted Intermolecular Hydrogen Atom Transfer

Joshua L. Zhu et al.

Summary: Stable acyl azolium salts can undergo intermolecular HAT reaction upon LED irradiation to afford ketones.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

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Article Chemistry, Physical

Acyl Azolium-Photoredox-Enabled Synthesis of β-Keto Sulfides

Michael J. Rourke et al.

Summary: Alpha-heteroatom functionalization is a crucial strategy for C-C bond formation in organic synthesis, achieved by adding a nucleophile to electrophilic functional groups, such as iminium ions, oxocarbenium ions, and their sulfur analogues - sulfenium ions. In this study, a photoredox-enabled radical Pummerer-type reaction was proposed, which involved the single-electron oxidation of a sulfide followed by alpha-deprotonation to form alpha-thioradicals. These radicals then participated in radical-radical coupling reactions with azolium-bound ketyl radicals, leading to functionalized additive Pummerer products and providing a new synthetic approach for highly functionalized sulfurous products.

ACS CATALYSIS (2023)

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Article Chemistry, Multidisciplinary

Organocatalytic C-H Functionalization of Simple Alkanes

Fen Su et al.

Summary: This study discloses the first organocatalytic direct functionalization/acylation of inert C(sp3)-H bonds of completely unfunctionalized alkanes. The approach involves N-heterocyclic carbene catalyst-mediated carbonyl radical intermediate generation and coupling with simple alkanes through the corresponding alkyl radical intermediates generated via a hydrogen atom transfer process. This method provides a new avenue for functionalization of challenging C-H bonds.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

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Article Chemistry, Multidisciplinary

Resurgence and advancement of photochemical hydrogen atom transfer processes in selective alkane functionalizations

Liang Chang et al.

Summary: The selective functionalization of alkanes has been a long-standing challenge in organic synthesis. Recent advancements in photoredox catalysis have provided exciting opportunities to trigger hydrogen atom transfer (HAT) processes and achieve radical-mediated functionalizations in a more selective manner. This perspective highlights the development of photocatalytic systems and discusses current challenges and future prospects in this field.

CHEMICAL SCIENCE (2023)

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Article Chemistry, Applied

Combined Photoredox and Carbene Catalysis for the Synthesis of γ-Aryloxy Ketones

Pengzhi Wang et al.

Summary: The research presents a method for synthesizing gamma-aryloxyketones via combined NHC/photoredox catalysis, where an α-aryloxymethyl radical is coupled with styrene derivatives and then with an azolium radical to produce the desired products.

ADVANCED SYNTHESIS & CATALYSIS (2022)

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Review Chemistry, Multidisciplinary

Alkoxy Radicals See the Light: New Paradigms of Photochemical Synthesis

Liang Chang et al.

Summary: This review comprehensively summarizes the recent progress in alkoxy radical-mediated transformations under visible light irradiation. The mechanisms of alkoxy radical generation and their impact on synthetic utilizations are discussed. The catalytic generation of alkoxy radicals from abundant alcohols is still in the early stage, but holds great potential.

CHEMICAL REVIEWS (2022)

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Review Chemistry, Multidisciplinary

Photoredox-Catalyzed C-H Functionalization Reactions

Natalie Holmberg-Douglas et al.

Summary: The fields of C-H functionalization and photoredox catalysis have gained significant interest and utility in various scientific disciplines. This review focuses on the use of photoredox catalysis in C-H functionalization reactions, highlighting both inorganic/organometallic and organic-based photoredox catalytic systems. The subdivision by reaction class (sp(2) or sp(3) C-H functionalization) provides perspective and tactical strategies for synthetic applications.

CHEMICAL REVIEWS (2022)

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Article Chemistry, Organic

Visible-Light-Driven Bisfunctionalization of Unactivated Olefins via the Merger of Proton-Coupled Electron Transfer and Carbene Catalysis

Bei Zhang et al.

Summary: In this study, a novel NHC and photo-co-catalyzed alkylacylation of olefins using diazo esters as radical source is reported, presenting a new idea for transient radical generation with the only byproduct being N-2. Compared to previous methods, this process shows great atom economy with reduced discard fragments.

ORGANIC LETTERS (2022)

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Article Chemistry, Physical

Combined Photoredox and Carbene Catalysis for the Synthesis of α-Amino Ketones from Carboxylic Acids

Xiaochen Wang et al.

Summary: We report a mild and operationally simple method for the direct acylation of α-amino C(sp(3))-H bonds from carboxylic acids. The method combines carbene and photoredox catalysis and successfully synthesizes structurally diverse α-amino ketones through the cross-coupling reactions between a wide range of carboxylic acids and readily available N-alkyl anilines. This method demonstrates a broad substrate scope and compatibility with various functional groups.

ACS CATALYSIS (2022)

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Review Chemistry, Multidisciplinary

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C-H Bonds Elaboration

Luca Capaldo et al.

Summary: Direct photocatalyzed hydrogen atom transfer (d-HAT) is a preferred method for the synthesis of aliphatic C-H bonds in organic compounds. Selective C-H bond elaboration can be achieved by choosing suitable hydrogen abstractors and reaction additives. This review provides a comprehensive survey of the synthetic applications of photocatalyzed d-HAT.

CHEMICAL REVIEWS (2022)

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Article Chemistry, Multidisciplinary

Synthesis of Cyclohexanones by a Tandem Photocatalyzed Annulation

Anna Bay et al.

Summary: This study presents a novel tandem carbene and photoredox-catalyzed process for the synthesis of substituted cycloalkanones, offering a new approach for constructing important cyclic scaffolds.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Multidisciplinary Sciences

Carbene and photocatalyst-catalyzed decarboxylative radical coupling of carboxylic acids and acyl imidazoles to form ketones

Shi-Chao Ren et al.

Summary: This study reports a decarboxylative radical coupling of carboxylic acids and acyl imidazoles catalyzed by an N-heterocyclic carbene and photocatalyst. The carboxylic acids serve as direct radical precursors, and suitable acyl imidazoles can also be generated in situby a reaction with CDI. The method is extended to three-component coupling by using alkenes as a third coupling partner via a radical relay process. The mild reaction conditions, simplicity, and use of easily available starting materials make this method a powerful strategy for constructing complex ketones and modifying natural products and medicines.

NATURE COMMUNICATIONS (2022)

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Article Multidisciplinary Sciences

Stereoretentive cross-coupling of chiral amino acid chlorides and hydrocarbons through mechanistically controlled Ni/Ir photoredox catalysis

Geun Seok Lee et al.

Summary: In this study, an efficient method for the stereoretentive direct cross-coupling of chiral amino acid chlorides and unactivated C(sp(3))-H hydrocarbons was achieved via photoredox catalysis. The strategic generation of an N-acyllutidinium intermediate facilitated the synthesis of chiral amino ketones with retention of stereochemistry.

NATURE COMMUNICATIONS (2022)

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Article Chemistry, Physical

Radical NHC Catalysis

Kun Liu et al.

Summary: Radical/radical cross-coupling reactions are efficient and direct methods for constructing chemical bonds. The widespread application of persistent radical effect (PRE) has been limited by the fact that the known types of transient radicals far outnumber the known types of persistent radicals. Recent research has focused on developing efficient cross-coupling reactions between transient radicals, and transition-metal catalysis has been successfully used to prolong radical lifetimes, enabling their utilization in formal radical/radical cross-couplings.

ACS CATALYSIS (2022)

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Editorial Material Chemistry, Multidisciplinary

Asymmetric Catalysis in Radical Chemistry

David A. Nagib

CHEMICAL REVIEWS (2022)

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Review Chemistry, Multidisciplinary

Single-electron carbene catalysis in redox processes

Anna Bay et al.

Summary: Chemists have used the polarity reversal reactivity of N-heterocyclic carbenes (NHCs) to build key chemical bonds, and their redox properties enable the synthesis of stable radical species. This has greatly contributed to the field of synthetic chemistry and the revival of radical chemistry.

TRENDS IN CHEMISTRY (2022)

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Review Chemistry, Organic

The Merger of Photocatalyzed Hydrogen Atom Transfer with Transition Metal Catalysis for C-H Functionalization of Alkanes and Cycloalkanes

Ziqi Ye et al.

Summary: This article summarizes recent advances in dual photo-induced HAT and transition metal catalysis for C-H functionalization of alkanes and cycloalkanes. By combining the advantages of light and metal, this method solves the problem of chemical inertness in straight-chain alkanes and cycloalkanes, enabling a variety of selective synthetic reactions.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2021)

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Review Chemistry, Multidisciplinary

Visible-Light-Induced Homolysis of Earth-Abundant Metal-Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis

Youssef Abderrazak et al.

Summary: The mainstream applications of visible-light photoredox catalysis mainly involve precious metal Ru-II or Ir-III complexes or organic dyes with low photostability. Earth-abundant metal-based (MLn)-L-n-type complexes are evolving rapidly as alternative photocatalysts that offer economic and ecological advantages and access to complementary inner-sphere mechanistic modes, transcending the inherent limitations of ultrashort excited-state lifetimes. The process of visible-light-induced homolysis (VLIH) involves the formation of light-absorbing ligated metal-substrate complexes that undergo homolytic cleavage for further transformations.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Physical

Carbene-Catalyzed Alkylation of Carboxylic Esters via Direct Photoexcitation of Acyl Azolium Intermediates

Shi-Chao Ren et al.

Summary: A carbene-catalyzed reductive coupling reaction of carboxylic esters and substituted Hantzsch esters has been disclosed, which is promoted by visible light irradiation and allows for incorporation of sophisticated structures, including those found in medicines, into ketone molecules under mild conditions.

ACS CATALYSIS (2021)

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Article Chemistry, Physical

Light-Driven N-Heterocyclic Carbene Catalysis Using Alkylborates

Yukiya Sato et al.

Summary: This research developed a new method for radical-radical coupling, utilizing light-driven NHC organocatalysis to achieve this reaction, and generating alkyl radicals through borates for single electron transfer. This protocol enables cross-coupling between alkylborates and acyl imidazoles, as well as radical relay-type alkylacylations of alkenes with alkylborates and acyl imidazoles.

ACS CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis

Kun Liu et al.

Summary: N-Heterocyclic carbene (NHC) catalysis is a versatile tool in modern synthetic chemistry, often used in concert with a second catalytic moiety to expand reaction scope. Triple catalysis, merging three different catalytic modes in a single process, has been recently studied, allowing for the synthesis of complex compounds. In a reported study, alpha-C-H acylation of alkenes using NHC, sulfinate, and photoredox cooperative triple catalysis was achieved, highlighting the potential of such synergistic catalytic systems.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Renaissance of Homogeneous Cerium Catalysts with Unique Ce(IV/III) Couple: Redox-Mediated Organic Transformations Involving Homolysis of Ce(IV)-Ligand Covalent Bonds

Hayato Tsurugi et al.

Summary: Recent advances in the catalytic application of cerium complexes have been achieved through controlling the Ce(IV/III) redox couple. Cerium complexes can be used as catalysts by introducing supporting ligands around the coordination sphere of cerium and taking advantage of the photoresponsive properties of Ce(IV) and Ce(III) species. Overall, cerium complexes as new and promising homogeneous catalyst candidates for a variety of organic transformations under mild reaction conditions.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Multidisciplinary Sciences

Benzylic C-H acylation by cooperative NHC and photoredox catalysis

Qing-Yuan Meng et al.

Summary: Methods enabling site-selective acylation of sp3 C-H bonds in complex organic molecules are not well explored. Here, the authors present a direct and site-selective acylation of benzylic C-H bonds through the combination of N-heterocyclic carbene (NHC) and photoredox catalysis, offering options for preparing benzyl aryl ketones.

NATURE COMMUNICATIONS (2021)

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Article Chemistry, Multidisciplinary

Rapid and Direct Photocatalytic C(sp3)-H Acylation and Arylation in Flow

Daniele Mazzarella et al.

Summary: This study demonstrates a photocatalytic procedure for the acylation/arylation of unfunctionalized alkyl derivatives in flow, utilizing decatungstate anion and nickel catalyst to form C(sp(3))-C(sp(2)) bonds. The intensified conditions in flow reduce the reaction time significantly, without altering the reaction mechanism, accelerating the overall process.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Light-Driven Carbene Catalysis for the Synthesis of Aliphatic and α-Amino Ketones

Anna Bay et al.

Summary: This study reports the light-driven synthesis of aliphatic and alpha-amino ketones using single-electron NHC operators. Computational and experimental results show that the reactivity of the key radical intermediate depends on the substrate and can be modulated through steric and electronic parameters of the NHC. This methodology is showcased in the direct late-stage functionalization of amino acids and pharmaceutical compounds, highlighting the utility of single-electron NHC operators.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Multidisciplinary Sciences

Photocatalytic C-H activation and the subtle role of chlorine radical complexation in reactivity

Qiaomu Yang et al.

Summary: The reported carbon-hydrogen (C-H) activation of alkanes is actually mediated by the photocatalyst [NEt4](2)[CeCl6], and RO center dot are not intermediates. The generation of chlorine radical (Cl center dot) in the photocatalytic system is found to be the rate-limiting step. Density functional theory calculations support the formation of [Cl center dot][alcohol] adducts, which can manifest a masked RO center dot character.

SCIENCE (2021)

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Review Chemistry, Multidisciplinary

Synthetic Photoelectrochemistry

Joshua P. Barham et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids

Anna V. Bay et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Medicinal

One-Pot Formal Dehydrogenative Ketone Synthesis from Aldehydes and Non-activated Hydrocarbons

Kenzo Yahata et al.

CHEMICAL & PHARMACEUTICAL BULLETIN (2020)

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Article Chemistry, Multidisciplinary

Cooperative NHC and Photoredox Catalysis for the Synthesis of β-Trifluoromethylated Alkyl Aryl Ketones

Qing-Yuan Meng et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Synergistic Activation of Amides and Hydrocarbons for Direct C(sp3)-H Acylation Enabled by Metallaphotoredox Catalysis

Geun Seok Lee et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Physical

Light-Promoted Organocatalysis with N-Heterocyclic Carbenes

Andreas Mavroskoufis et al.

CHEMPHOTOCHEM (2020)

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Article Chemistry, Physical

Catalytic, Metal-Free Amide Synthesis from Aldehydes and Imines Enabled by a Dual-Catalyzed Umpolung Strategy under Redox-Neutral Conditions

Ming-Shang Liu et al.

ACS CATALYSIS (2020)

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Article Multidisciplinary Sciences

Metal-free photoinduced C(sp3)-H borylation of alkanes

Chao Shu et al.

NATURE (2020)

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Article Chemistry, Multidisciplinary

N-Heterocyclic carbene-catalyzed deaminative cross-coupling of aldehydes with Katritzky pyridinium salts

Inwon Kim et al.

CHEMICAL SCIENCE (2020)

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Article Chemistry, Multidisciplinary

N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes

Takuya Ishii et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Article Chemistry, Multidisciplinary

C-H Alkylation via Multisite-Proton-Coupled Electron Transfer of an Aliphatic C-H Bond

Carla M. Morton et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Article Chemistry, Multidisciplinary

What Are the Radical Intermediates in Oxidative Carbene Organocatalysis?

Vianney Regnier et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Review Chemistry, Multidisciplinary

Advances in Development of C-H Activation/Functionalization Using a Catalytic Directing Group

Omer K. Rasheed et al.

CHEMISTRYSELECT (2018)

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Review Chemistry, Multidisciplinary

A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry

Carlo Sambiagio et al.

CHEMICAL SOCIETY REVIEWS (2018)

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Article Multidisciplinary Sciences

Direct arylation of strong aliphatic C-H bonds

Ian B. Perry et al.

NATURE (2018)

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Article Multidisciplinary Sciences

Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis

Anhua Hu et al.

SCIENCE (2018)

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Review Chemistry, Multidisciplinary

Lanthanide Photocatalysis

Yusen Qiao et al.

ACCOUNTS OF CHEMICAL RESEARCH (2018)

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Article Chemistry, Multidisciplinary

Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis

Laura K. G. Ackerman et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2018)

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Editorial Material Chemistry, Multidisciplinary

Strong C(sp3)-H Arylation by Synergistic Decatungstate Photo-HAT and Nickel Catalysis

Dong-Mei Yan et al.

CHEM (2018)

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Review Chemistry, Organic

Hydrogen Atom Transfer (HAT): A Versatile Strategy for Substrate Activation in Photocatalyzed Organic Synthesis

Luca Capaldo et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2017)

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Review Chemistry, Multidisciplinary

The merger of transition metal and photocatalysis

Jack Twilton et al.

NATURE REVIEWS CHEMISTRY (2017)

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Review Chemistry, Multidisciplinary

Evolution of C-H Bond Functionalization from Methane to Methodology

John F. Hartwig

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

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Review Chemistry, Multidisciplinary

Decatungstate Anion for Photocatalyzed Window Ledge Reactions

Davide Ravelli et al.

ACCOUNTS OF CHEMICAL RESEARCH (2016)

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Review Chemistry, Multidisciplinary

Dual Catalysis Strategies in Photochemical Synthesis

Kazimer L. Skubi et al.

CHEMICAL REVIEWS (2016)

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Article Chemistry, Multidisciplinary

Visible-Light-Promoted Activation of Unactivated C(sp3)-H Bonds and Their Selective Trifluoromethylthiolation

Satobhisha Mukherjee et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

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Article Chemistry, Multidisciplinary

The Hexachlorocerate(III) Anion: A Potent, Benchtop Stable, and Readily Available Ultraviolet A Photosensitizer for Aryl Chlorides

Haolin Yin et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

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Article Chemistry, Multidisciplinary

Dual Catalysis Sees the Light: Combining Photoredox with Organo-, Acid, and Transition-Metal Catalysis

Matthew N. Hopkinson et al.

CHEMISTRY-A EUROPEAN JOURNAL (2014)

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Review Chemistry, Multidisciplinary

Catalytic Functionalization of C(sp2)-H and C(sp3)-H Bonds by Using Bidentate Directing Groups

Guy Rouquet et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2013)

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Review Chemistry, Multidisciplinary

Photoorganocatalysis. What for?

Davide Ravelli et al.

CHEMICAL SOCIETY REVIEWS (2013)

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Review Chemistry, Multidisciplinary

Visible-Light Photoredox Catalysis

Jun Xuan et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2012)

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Article Chemistry, Multidisciplinary

Atom-Economical Synthesis of Unsymmetrical Ketones through Photocatalyzed C-H Activation of Alkanes and Coupling with CO and Electrophilic Alkenes

Ilhyong Ryu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2011)

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Editorial Material Chemistry, Multidisciplinary

C-H Functionalization in organic synthesis

Huw M. L. Davies et al.

CHEMICAL SOCIETY REVIEWS (2011)

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Review Chemistry, Multidisciplinary

Visible light photoredox catalysis: applications in organic synthesis

Jagan M. R. Narayanam et al.

CHEMICAL SOCIETY REVIEWS (2011)

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Editorial Material Chemistry, Multidisciplinary

Introduction to Selective Functionalization of C-H Bonds

Robert H. Crabtree

CHEMICAL REVIEWS (2010)

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Article Chemistry, Multidisciplinary

Visible light photocatalysis as a greener approach to photochemical synthesis

Tehshik P. Yoon et al.

NATURE CHEMISTRY (2010)

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Editorial Material Chemistry, Multidisciplinary

Photoredox Catalysis with Visible Light

Kirsten Zeitler

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2009)

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Review Chemistry, Multidisciplinary

Selective alkane transformations via radicals and radical cations: Insights into the activation step from experiment and theory

AA Fokin et al.

CHEMICAL REVIEWS (2002)

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Photoinduced cerium-catalyzed C-H acylation of unactivated alkanes

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