4.7 Article

Recent Advances in Employing Catalytic Donors and Acceptors in Electron Donor-Acceptor Complex Photochemistry

Related references

Note: Only part of the references are listed.
Article Chemistry, Multidisciplinary

Fluorinated Sulfinates as Source of Alkyl Radicals in the Photo-Enantiocontrolled β-Functionalization of Enals

Ricardo Rodriguez et al.

Summary: In this study, a convenient strategy using gem-difluorinated sulfinates as upgrading-masks is reported, which allows the decomposition of precursors into corresponding alkyl radicals. The stereocontrolled light-driven insertion of gem-difluoro derivatives into unsaturated aldehydes is achieved.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Review Chemistry, Multidisciplinary

Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis

Matthew J. Genzink et al.

Summary: Asymmetric photocatalysis is a major research topic in contemporary synthetic organic chemistry. However, the discovery of general strategies for highly enantioselective photochemical reactions has been a recent development, leading to a somewhat limited variety of stereocontrolled photoreactions. This review summarizes the chiral catalyst structures that have been studied for solution-phase asymmetric photochemistry, providing insight into the logic required for highly effective stereocontrolled photocatalysis.

CHEMICAL REVIEWS (2022)

Review Chemistry, Multidisciplinary

Aryl Transfer Strategies Mediated by Photoinduced Electron Transfer

Anthony R. Allen et al.

Summary: This review summarizes the progress in radical aryl migration enabled by photochemical methods, particularly photoredox catalysis, since 2015. Special attention is given to describing the scope, mechanism, and synthetic applications of each method.

CHEMICAL REVIEWS (2022)

Review Chemistry, Multidisciplinary

Visible Light-Induced Transition Metal Catalysis

Kelvin Pak Shing Cheung et al.

Summary: Visible light-induced transition metal catalysis has emerged as an important development in organic photocatalysis, leading to unprecedented transformations and improvements of known reactions. This method utilizes a single catalytic cycle to harness photon energy, and synergistically combines catalyst-substrate interaction with photoinduced processes.

CHEMICAL REVIEWS (2022)

Article Chemistry, Organic

Aerobic Oxidative EDA Catalysis: Synthesis of Tetrahydroquinolines Using an Organocatalytic EDA Active Acceptor

August Runemark et al.

Summary: This paper reports a catalytic electron donor-acceptor (EDA) complex for visible light-driven annulation reaction between alkylated alkenes and N,N-substituted dialkyl anilines. Investigations into the mechanism reveal the rare example of a catalytic acceptor in photoactive EDA complexes that can give selective functionalization of aromatic amines under mild photochemical conditions.

JOURNAL OF ORGANIC CHEMISTRY (2022)

Article Chemistry, Multidisciplinary

Photochemical Organocatalytic Benzylation of Allylic C-H Bonds

Emilien Le Saux et al.

Summary: We report a radical-based organocatalytic method for the direct benzylation of allylic C-H bonds. This method uses nonfunctionalized allylic substrates and readily available benzyl radical precursors, and is driven by visible light. By controlling two orthogonal radical generation paths, it enables the selective coupling of allylic and benzylic radicals, thus expanding the synthetic potential of organic chemistry.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Chemistry, Organic

Radical Perfluoroalkylation Enabled by a Catalytically Generated Halogen Bonding Complex and Visible Light Irradiation

Tarannum Tasnim et al.

Summary: Using a substituted hydroquinone catalyst to promote radical perfluoroalkylation reactions, the mechanism involves the formation of a visible light-absorbing halogen bonding complex, leading to the opening of novel synthetic pathways.

ORGANIC LETTERS (2022)

Article Chemistry, Physical

N-Heterocyclic Carbene-Photocatalyzed Tricomponent Regioselective 1,2-Diacylation of Alkenes Illuminates the Mechanistic Details of the Electron Donor-Acceptor Complex-Mediated Radical Relay Processes

Shengfei Jin et al.

Summary: Progress in developing photocatalytic reactions requires a detailed understanding of the underlying mechanisms, especially those involving electron donor-acceptor complexes. This study reports a new method for regioselective installation of two different acyl groups through photocatalytic alkene 1,2-diacylation. The research highlights the central role of electron donor-acceptor complexes in mediating the photoinduced charge transfer process and sheds light on the catalytic activities of N-heterocyclic carbenes in radical reactions.

ACS CATALYSIS (2022)

Review Chemistry, Multidisciplinary

Strategic Use of Visible-Light Photoredox Catalysis in Natural Product Synthesis

Spencer P. Pitre et al.

Summary: Recent progress in visible light photocatalytic reactions has revitalized the use of photochemistry in the synthesis of complex organic molecules. This review examines total syntheses published by the end of 2020 that employ visible-light photoredox catalysis, providing insights on functional group compatibility and synthetic strategies.

CHEMICAL REVIEWS (2022)

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)

Review Chemistry, Multidisciplinary

Enantioselective Photochemical Reactions Enabled by Triplet Energy Transfer

Johannes Grosskopf et al.

Summary: This review provides a comprehensive survey on enantioselective photochemical reactions achieved through triplet sensitization. It is shown that highly selective enantioselective photochemical reactions can be achieved by using appropriate chiral sensitizers or a dual catalytic approach.

CHEMICAL REVIEWS (2022)

Article Chemistry, Multidisciplinary

Tetrachlorophthalimides as Organocatalytic Acceptors for Electron Donor-Acceptor Complex Photoactivation

Wei Zhou et al.

Summary: In this study, it was found that tetrachlorophthalimides can act as effective organocatalytic acceptors, triggering radical reactions not amenable to previous catalytic methods. This finding allowed the development of mechanistically distinct radical reactions and the evaluation of catalytic cycle via quantum yield measurements.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Chemistry, Organic

Metal-Free Iodoperfluoroalkylation: Photocatalysis versus Frustrated Lewis Pair Catalysis

Lucas Helmecke et al.

Summary: The article compares two metal-free catalytic iodoperfluoro-alkylation protocols, where frustrated Lewis pairs or phosphines/phosphites under visible light irradiation efficiently mediate the functionalization of non-activated alkenes and alkynes. A comprehensive account of the corresponding substrate scopes and insights into the mechanistic details of both reaction pathways are provided.

SYNTHESIS-STUTTGART (2021)

Article Chemistry, Multidisciplinary

Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins

Claire G. Page et al.

Summary: This study presents a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. A unique mechanism involving a charge-transfer complex formed between an alkene, alpha-chloroamide, and flavin hydroquinone ensures radical formation only occurs when both substrates are present within the protein active site. This work demonstrates the potential for new biocatalytic transformations enabled by photoenzymatic catalysis through previously unknown electron transfer mechanisms.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Multidisciplinary

Photocatalytic decarboxylative alkylations of C(sp3)-H and C(sp2)-H bonds enabled by ammonium iodide in amide solvent

Guang-Zu Wang et al.

Summary: The method uses ammonium iodide salt in amide solvent for the visible light irradiation catalysis, achieving efficient synthesis of redox active esters with simplicity, practicality, and broad substrate scope, showcasing the synthetic power of photocatalysis through transiently assembled chromophore and potentially inspiring further developments in low cost photocatalysis.

SCIENCE CHINA-CHEMISTRY (2021)

Article Chemistry, Multidisciplinary

Photoenzymatic Synthesis of α-Tertiary Amines by Engineered Flavin-Dependent Ene-Reductases

Xin Gao et al.

Summary: This study demonstrates that engineered flavin-dependent 'ene'-reductases (EREDs) can catalyze radical additions into oximes with high stereoselectivity to prepare alpha-tertiary amines, which are common in pharmaceutical molecules. Two evolved EREDs were competent catalysts for this transformation, and mechanistic studies revealed the role of oximes in the enzyme templated charge-transfer complex. The products can be further derivatized for the synthesis of various motifs, showcasing the versatility of ERED photoenzymatic catalysis in organic synthesis.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Organic

Photoinduced α-Alkenylation of Katritzky Salts: Synthesis of β,γ-Unsaturated Esters

Chao-Shen Zhang et al.

Summary: A simple NaI-involved photoinduced deaminative alkenylation was proposed for the synthesis of beta,gamma-unsaturated esters without the need for photocatalysts and additives. Density functional theory study revealed that the electrostatic interaction of NaI with Katritzky salts is crucial in forming the photoactive electron donor-acceptor complex.

ORGANIC LETTERS (2021)

Article Chemistry, Organic

Organophotoredox-Catalyzed Three-Component Coupling of Heteroatom Nucleophiles, Alkenes, and Aliphatic Redox Active Esters

Shotaro Shibutani et al.

Summary: This method describes a visible-light-mediated organo-photoredox catalytic process for vicinal difunctionalization of alkenes using heteroatom nucleophiles and aliphatic redox active esters. A wide range of heteroatom nucleophiles can be used for this reaction, allowing the forging of C(sp(3))-C(sp(3)) and C(sp(3))-heteroatom bonds with high regioselectivity in a single step.

ORGANIC LETTERS (2021)

Article Chemistry, Multidisciplinary

Visible-Light-Induced Selective Photolysis of Phosphonium Iodide Salts for Monofluoromethylations

Qiang Liu et al.

Summary: The sigma-hole effect is utilized to facilitate the photolysis of phosphonium iodide salts, selectively generating fluoromethyl radicals, allowing for mono-, di-, and trifluoromethylation reactions using fluoromethylphosphonium salts.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Multidisciplinary

A General Organocatalytic System for Electron Donor-Acceptor Complex Photoactivation and Its Use in Radical Processes

Eduardo de Pedro Beato et al.

Summary: The study introduces a modular class of organic catalysts that can form photoactive electron donor-acceptor complexes with radical precursors. Excitation with visible light generates open-shell intermediates, allowing for the development of mechanistically distinct radical reactions encompassing redox-neutral and net-reductive processes. The organic catalysts demonstrate the ability to turn over and iteratively drive every catalytic cycle, enabling direct radical functionalization and enantioselective radical catalysis.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Organic

B(C6F5)3-Catalyzed Electron Donor-Acceptor Complex-Mediated Aerobic Sulfenylation of Indoles under Visible-Light Conditions

Wenkai Yuan et al.

Summary: An efficient aerobic oxidative C-S cross-coupling reaction of thiophenol with indoles was developed using B(C6F5)(3) as a single-electron oxidant, producing a wide range of diaryl sulfides in good yields. The formation of an electron donor-acceptor complex between B(C6F5)(3) and indoles facilitated the photoinduced single-electron transfer from indole substrates to the B(C6F5)(3) catalyst. This protocol demonstrates a new reaction model for oxidative C-S cross-coupling reactions.

ORGANIC LETTERS (2021)

Article Chemistry, Organic

Decarboxylative N-Alkylation of Azoles through Visible-Light-Mediated Organophotoredox Catalysis

Rino Kobayashi et al.

Summary: An organophotoredox-catalyzed decarboxylative cross-coupling between azole nucleophiles and aliphatic carboxylic acid-derived redox-active esters is demonstrated. This reaction efficiently installs various alkyl fragments onto the nitrogen atom of azole nucleophiles under mild and transition-metal-free conditions. The use of a pyridinium additive successfully inhibits the formation of elimination byproducts from the carbocation intermediate, making this reaction applicable to the synthesis of molecule with potential protein-degrading properties.

ORGANIC LETTERS (2021)

Article Chemistry, Physical

Visible-Light-Induced Oxazoline Formations from N-Vinyl Amides Catalyzed by an Ion-Pair Charge-Transfer Complex

Rui Sun et al.

Summary: The ion-pair charge-transfer (IPCT) complex-induced visible-light photoredox catalytic reactions have been successfully demonstrated in cyclization-methoxylation of N-vinyl amides, using a heteroarenium iodide as the photocatalyst. This environmentally friendly synthetic route can be extended to various reactions, providing a wide range of applications. The mechanism involves the existence of the IPCT absorption band in the visible region for the heteroarenium iodide, responsible for the observed reactivity.

ACS CATALYSIS (2021)

Article Chemistry, Physical

Photocatalytic C(sp3)-O/N Cross-Couplings by NaI-PPh3/CuBr Cooperative Catalysis: Computational Design and Experimental Verification

Run-Han Li et al.

Summary: Photocatalytic coupling reactions have rapidly developed in the field of organic synthesis. A novel metallaphotoredox catalysis utilizing a NaI-PPh3 photoredox catalyst and Cu(I) catalyst was designed and evaluated, achieving high yields of C(sp(3))-O/N cross-couplings of alkyl N-hydroxyphthalimide esters with phenols/secondary amines under mild conditions with only blue light irradiation. This strategy provides a facile and economic route for C(sp(3))-X cross-coupling reactions while also offering a clear mechanistic understanding.

ACS CATALYSIS (2021)

Article Chemistry, Organic

Visible-light-induced iodine-anion-catalyzed decarboxylative/deaminative C-H alkylation of enamides

Jia-Xin Wang et al.

Summary: A visible-light-induced iodine-anion-catalyzed C-H stereoselective alkylation of enamides has been developed, delivering various functionalized enamides with excellent functional group tolerance. The reaction proceeds via photoactivation of the transiently assembled chromophores, avoiding the use of exogenous precious photoredox catalysts.

ORGANIC CHEMISTRY FRONTIERS (2021)

Article Chemistry, Organic

Photocatalytic decarboxylative alkylation of silyl enol ether and enamide with N-(acyloxy)phthalimide using ammonium iodide

Can Liu et al.

Summary: Enamides and silyl enol ethers were alkylated to produce N-acyl imines and ketones using a catalytic amount of N-tetrabutylammonium iodide under irradiation with purple light-emitting diodes. A variety of tertiary, secondary, and primary alkylation products were achieved with good yields and tolerance of functional groups, showcasing the practicality of using alkyl carboxylates as alkyl sources in organic synthesis without the need for expensive metal catalysts.

ORGANIC CHEMISTRY FRONTIERS (2021)

Review Chemistry, Multidisciplinary

Direct excitation strategy for radical generation in organic synthesis

Yuto Sumida et al.

Summary: Visible-light-mediated chemical processes have been extensively studied, leading to cutting-edge synthetic chemistry by controlling radical generation and excited-state transformations. While photoredox chemistry is important, it often involves photocatalysts and redox processes, complicating reactions. A breakthrough in this field is the development of a system free of photocatalysts, providing more straightforward and energetically efficient methods.

CHEMICAL SOCIETY REVIEWS (2021)

Article Chemistry, Organic

Visible Light-Promoted Phosphine-Catalyzed Difluoroalkylation of Arenes and Heterocycles

Heng Lu et al.

JOURNAL OF ORGANIC CHEMISTRY (2020)

Article Chemistry, Multidisciplinary

Organophotoredox-Catalyzed Decarboxylative C(sp3)-O Bond Formation

Shotaro Shibutani et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

Review Chemistry, Multidisciplinary

Synthetic Methods Driven by the Photoactivity of Electron Donor-Acceptor Complexes

Giacomo E. M. Crisenza et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

Article Multidisciplinary Sciences

Photoenzymatic enantioselective intermolecular radical hydroalkylation

Xiaoqiang Huang et al.

NATURE (2020)

Article Chemistry, Multidisciplinary

Photoenzymatic Generation of Unstabilized Alkyl Radicals: An Asymmetric Reductive Cyclization

Phillip D. Clayman et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

Article Chemistry, Multidisciplinary

Exploiting single-electron transfer in Lewis pairs for catalytic bond-forming reactions

Yoshitaka Aramaki et al.

CHEMICAL SCIENCE (2020)

Article Multidisciplinary Sciences

Photoexcitation of flavoenzymes enables a stereoselective radical cyclization

Kyle F. Biegasiewicz et al.

SCIENCE (2019)

Article Chemistry, Multidisciplinary

Deoxygenative Deuteration of Carboxylic Acids with D2O

Muliang Zhang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

Article Chemistry, Multidisciplinary

Stereocontrolled Synthesis of 1,4-Dicarbonyl Compounds by Photochemical Organocatalytic Acyl Radical Addition to Enals

Giulio Goti et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

Article Chemistry, Multidisciplinary

Bioinspired Radical Stetter Reaction: Radical Umpolung Enabled by Ion-Pair Photocatalysis

Tobias Morack et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

Article Chemistry, Multidisciplinary

Photochemical generation of radicals from alkyl electrophiles using a nucleophilic organic catalyst

Bertrand Schweitzer-Chaput et al.

NATURE CHEMISTRY (2019)

Article Chemistry, Multidisciplinary

Visible light promoted fluoroalkylation of alkenes and alkynes using 2-bromophenol as a catalyst

Erlin Zhu et al.

CHEMICAL COMMUNICATIONS (2019)

Article Chemistry, Multidisciplinary

Visible-Light-Promoted Dearomative Fluoroalkylation of beta-Naphthols through Intermolecular Charge Transfer

Quanping Guo et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

Article Multidisciplinary Sciences

A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes

Muliang Zhang et al.

NATURE COMMUNICATIONS (2018)

Article Chemistry, Medicinal

Photo-Induced Atom-Transfer Radical Reactions Using Charge-Transfer Complex between Iodine and Tertiary Amine

Eito Yoshioka et al.

CHEMICAL & PHARMACEUTICAL BULLETIN (2017)

Article Chemistry, Multidisciplinary

Metal-Free, Visible Light-Photocatalyzed Synthesis of Benzo[b]phosphole Oxides: Synthetic and Mechanistic Investigations

Valentin Quint et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

Article Multidisciplinary Sciences

Accessing non-natural reactivity by irradiating nicotinamide-dependent enzymes with light

Megan A. Emmanuel et al.

NATURE (2016)

Article Multidisciplinary Sciences

A scalable and operationally simple radical trifluoromethylation

Joel W. Beatty et al.

NATURE COMMUNICATIONS (2015)

Article Chemistry, Multidisciplinary

Enantioselective direct α-alkylation of cyclic ketones by means of photo-organocatalysis

Elena Arceo et al.

CHEMICAL SCIENCE (2014)

Review Multidisciplinary Sciences

Engineering the third wave of biocatalysis

U. T. Bornscheuer et al.

NATURE (2012)