Electron Donor-acceptor Complexes Research Articles

Proton-Coupled Electron Transfer Ring Opening of Cycloalkanols Followed by a Giese Radical Addition Enabled by an Electron Donor-Acceptor Complex.

Herein, we describe the formation of an electron donor-acceptor (EDA) complex between electron-rich cycloalkanols and electron-deficient alkenes that triggers the proton-coupled electron transfer ring opening of strained and unstrained cycloalkanols without the need for an external photocatalyst. This activation generates a remote alkyl radical that undergoes a Giese reaction with the Michael acceptor in an efficient manner. Mechanistic investigations corroborate both the formation of the EDA complex and the consecutive Giese reaction.

Photoinduced Alkenylation of Alkenyl Sulfones with EDA Complexes between NHPI Esters and HE

AbstractA novel alkenylation reaction between N‐hydroxyphthalimide (NHPI) esters and alkenyl sulfones is reported. It undergoes the formation of electron donor‐acceptor (EDA) complex and a series of alkenes are obtained in good to excellent yields. It has the advantages of simple operation, mild reaction conditions, and metal‐free.

Access to Benzyl Oxindoles via Electron Donor‐Acceptor Complex Photoactivation Using Thianthrenium Salts and Potassium Carbonate

AbstractA photochemical synthesis of biologically relevant benzyl oxindoles is presented via electron‐donor acceptor (EDA) complex strategy. This exogenous photocatalyst‐free method describes the formation of a new electron donor‐acceptor complex based on potassium carbonate and thianthrenium salts for C(sp2)−C(sp3) bond formation. This transition‐metal free reaction allows a rapid increase in oxindoles molecular complexity chemical space, tolerating different functional groups as well as sophisticated biomolecules. The scalability and sustainability of this method is highlighted by an important waste recovery protocol. Mechanistic investigations support the formation of an EDA complex that induces a radical chain, and the applicability of this method is showcased by straightforward derivatization reactions.

Visible-Light-Promoted C3-Sulfenylindoles with Arylsulfonyl Chlorides via Electron Donor-Acceptor Complex.

In this study, we present an efficient approach for the synthesis of 3-sulfenyl indoles through an electron donor-acceptor (EDA) complex-promoted photoreaction. This sulfenylation reaction leverages sulfonyl chlorides as the sulfur source and employs PPh3 as the reductant without the need for any transition-metal catalyst or photocatalyst. At the same time, the relaxation process of the excited EDA complex was theoretically investigated at the method and multiconfiguration second-order perturbation//complete active space self-consistent field/PCM level of theory, which involves the π bond of indoles injecting an electron to the antibonding orbital of the S-Cl bond in arylsulfonyl chlorides.

Photoreduction of Trifluoromethyl Group: Lithium Ion Assisted Fluoride-Coupled Electron Transfer from EDA Complex.

Photoinduced single-electron reduction is an efficient method for the mono-selective activation of the C-F bond on a trifluoromethyl group to construct a difluoroalkyl group. We have developed an electron-donor-acceptor (EDA) complex mediated single-electron transfer (EDA-SET) of α,α,α-trifluoromethyl arenes in the presence of lithium salt to give α,α-difluoroalkylarenes. The C-F bond reduction was realized by lithium iodide and triethylamine, two common feedstock reagents. Mechanistic studies revealed the generation of a α,α-difluoromethyl radical by single-electron reduction and defluorination, followed by the radical addition to alkenes. Lithium salt interacted with the fluorine atom to promote the photoinduced reduction mediated by the EDA complex. Computational studies indicated that the lithium-assisted defluorination and the single-electron reduction occurred concertedly. We call this phenomenon fluoride-coupled electron transfer (FCET). FCET is a novel approach to C-F bond activation for the synthesis of organofluorine compounds.

Visible-Light-Driven Germyl Radical Generation via EDA-Catalyzed ET-HAT Process.

We have established a facile and efficient protocol for the generation of germyl radicals by employing photo-excited electron transfer (ET) in an electron donor-acceptor (EDA) complex to drive hydrogen-atom transfer (HAT) from germyl hydride (R3GeH). Using a catalytic amount of EDA complex of commercially available thiol and benzophenone derivatives, the ET-HAT cycle smoothly proceeds simply upon blue-light irradiation without any transition metal or photocatalyst. This protocol also affords silyl radical from silyl hydride.

Perfluoroalkylation Reactions by Electron Donor‐Acceptor Complexes: Recent Advances

This Perspective analyses the perfluoroalkylation reactions by electron donor‐acceptor (EDA) complexes since 2018, while summarizes, in Tables 1‐3, the vast majority of representative perfluoroalkylation reactions of various classes of organic compounds by EDA complexes and halogen‐bonding interactions. Numerous intriguing reaction methodologies and valuable synthetic instances have emerged. We aim to delve into these new examples comprehensively, while also contemplating the future directions in the field. Subsequent sections will elaborate on the perfluoroalkylation of (hetero)aromatic compounds, carbon‐carbon multiple bonds, perfluoroalkylation of carbonyl compounds, and perfluoroalkylation of isocyanides, covering their synthetic scope and mechanistic insights.

Visible-Light-Induced C-H Cyanoalkylation of Azauracils with Cycloketone Oxime Esters via Catalytic EDA Complex.

Photoexcitation electron donor-acceptor (EDA) complexes provide an effective approach to produce radicals under mild conditions, while the catalytic version of EDA complex photoactivation remains scarce. Herein, we report a visible-light-induced organophotocatalytic pathway for the cyanoalkylation of azauracils using inexpensive and readily available 1,4-diazabicyclo[2.2.2]octane (DABCO) as a catalytic electron donor. This synthetic method exhibits exceptional compatibility with various functional groups and presents 34 examples in high yields. The efficient cyanoalkylation offers an environmentally friendly and sustainable route toward enhancing the structural and functional diversity of azauracils.

Photodecarboxylative Radical Cascade Involving N-(Acyloxy)phthalimides for the Synthesis of Pyrazolones.

We disclose N'-arylidene-N-acryloyltosylhydrazides as novel skeletons for the synthesis of biologically relevant alkylated pyrazolones through a photoinduced radical cascade with N-(acyloxy)pthalimides as readily available alkyl surrogates. The reaction proceeds through the formation of a photoactivated electron donor-acceptor (EDA) complex between alkyl N-(acyloxy)phthalimide (NHPI) esters and LiI/PPh3 as a commercially available donor system. The reaction exhibits a broad scope and scalability, thereby enabling synthesis of a broad spectrum of functionally orchestrated alkylated pyrazolones under mild and transition-metal-free conditions.

Electron Donor-Acceptor Complex Driven Photocatalyst-Free Trifluoromethylation of Heterocycles.

Heterocyclic trifluoromethylation is efficiently initiated through a photochemical reaction utilizing an electron donor-acceptor (EDA) complex, proceeding smoothly without the use of photocatalysts, transition-metal catalysts, or additional oxidants. This method has been optimized through extensive experimentation, demonstrating its versatility and efficacy across various substrates, including quinoxalinones, coumarins, and indolones. Notably, this approach enables the practical synthesis of trifluoromethylated quinoxalinones on a gram scale. Mechanistic investigations that incorporate radical trapping and ultraviolet/visible spectroscopy, confirmed the formation of the an EDA complex and elucidated the reaction pathways. This study highlights the crucial role of EDA photoactivation in trifluoromethylation, significantly expanding the application scope of EDA complexes in chemical synthesis.

Photoinduced Site-Selective Aryl C-H Borylation with Electron-Donor-Acceptor Complex Derived from B2Pin2 and Isoquinoline.

Due to boron's metalloid properties, aromatic boron reagents are prevalent synthetic intermediates. The direct borylation of aryl C-H bonds for producing aromatic boron compounds offers an appealing, one-step solution. Despite significant advances in this field, achieving regioselective aryl C-H bond borylation using simple and readily available starting materials still remains a challenge. In this work, we attempted to enhance the reactivity of the electron-donor-acceptor (EDA) complex by selecting different bases to replace the organic base (NEt3) used in our previous research. To our delight, when using NH4HCO3 as the base, we have achieved a mild visible-light-mediated aromatic C-H bond borylation reaction with exceptional regioselectivity (rr > 40:1 to single isomers). Compared with our previous borylation methodologies, this protocol provides a more efficient and broader scope for aryl C-H bond borylation through the use of N-Bromosuccinimide. The protocol's good functional-group tolerance and excellent regioselectivity enable the functionalization of a variety of biologically relevant compounds and novel cascade transformations. Mechanistic experiments and theoretical calculations conducted in this study have indicated that, for certain arenes, the aryl C-H bond borylation might proceed through a new reaction mechanism, which involves the formation of a novel transient EDA complex.

Perfluoroalkylation of Triarylamines by EDA Complexes and Ulterior Sensitized [6π]-Electrocyclization to Perfluoroalkylated Endo-Carbazoles. Mechanistic and Photophysical Studies.

Blue LEDs-irradiation of a mixture of N,N,N',N'-tetramethylethylenediamine (TMEDA) and perfluoroalkyl iodides (RF-I) - Electron Donor Acceptor (EDA)-complex - in the presence of triphenylamines (TPAs) in an aqueous solvent mixture afforded mono-perfluoroalkylated triphenylamines (RF-TPA) in good yields. These RF-TPA were further subjected to acetone-sensitized [6π]-electrocyclization at 315 nm-irradiation affording exclusively perfluoroalkylated endo-carbazole derivatives (RF-CBz) in quantitative yields. Mechanistic studies and photophysical properties of products are studied.

Exploring Tunable Properties, Solvent-Modulated Dynamics, and Novel C(sp3)-H Activation Mechanisms in Electron Donor-Acceptor Complexes.

Electron donor-acceptor (EDA) complex photochemistry has emerged as a vibrant area in visible-light-mediated synthetic radical chemistry. However, theoretical insights into the reaction mechanisms remain limited. Our study investigates the influence of solvent polarity and halogen atom types on radical reaction pathways in EDA complexes. We demonstrate that solvent polarity modulates the charge transfer and spatial arrangement within EDA complexes, thereby influencing their stability and reaction kinetics. Iodide ions play a crucial role in facilitating free radical generation and stabilizing reaction intermediates. Different halogen atom types exhibit distinct effects on radical reactions. Variations in radical concentration and solvent environment further affect the pathway selectivity. Additionally, light conditions influence the free radical generation and pathway selectivity. Our findings enhance the understanding of EDA complex photochemistry and radical reactions, offering insights for organic synthesis and photochemistry applications.

Radical (Hydro)Sulfonylation of Alkenes Promoted by Formation of an Electron Donor–Acceptor Complex

Radical (Hydro)Sulfonylation of Alkenes Promoted by Formation of an Electron Donor–Acceptor Complex

Photodriven Radical Perfluoroalkylation-Thiolation of Unactivated Alkenes Enabled by Electron Donor-Acceptor Complex.

A clean and direct three-component radical 1,2-difunctionalization of various alkenes with perfluoroalkyl iodides and thiosulfonates enabled by the electron donor-acceptor complex has been developed under light illumination at room temperature. The approach offers a convenient and environmentally friendly route for the simultaneous incorporation of Csp3-Rf and Csp3-S bonds, affording valuable polyfunctionalized alkane derivatives containing fluorine and sulfur in satisfactory yields. Consequently, this methodology holds significant value and practicality in the field of organic synthesis.

A Computational Study of Photoinduced Borylation for Selected Boron Sources.

This research article uses density functional theory (DFT) to study photoinduced borylation. This work examined the electron donor-acceptor complex (EDA) of bis(catecholato)diboron with different redox-active leaving groups and bis(pinacol)diboron with aryl N-hydroxyphthalimide. The results of these DFT studies show the complex ratio of B2 cat2 and N, N-dimethylacetamide (DMA) should be 1 : 2 which is consistent with the experimental results in the literature. We further proposed a reaction mechanism and calculated the energies associated with each step.

Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis

AbstractVisible‐light‐activated organic reactions unlock novel avenues for complex molecular transformations, impossible under standard “thermal” conditions, which makes them powerful tools in the arsenal of synthetic chemistry. However, transition metal‐based or organic photoredox catalysts are often used to ensure productive absorption of visible light, which might be not desirable to medicinal chemistry and industry due to toxicity, low sustainability, and high cost of most photocatalysts. A more environmentally and economically benign approach is based on the formation of transient electron donor‐acceptor (EDA) complexes between two reagents or a reagent and an additive, that readily absorb visible light, acting as internal photosensitizers. Within the EDA complex‐based arylation strategies, chemical transformations are mediated by noncovalent interaction between two molecules, namely between electron‐poor aryl halides or their synthetic equivalents and electron‐rich nucleophilic reagents or additives. Moreover, besides stoichiometric EDA complexes between two molecules, EDA complex based organocatalysis can be achieved in certain cases through regeneration of the donor molecules in the course of the reaction. Photoexcitation of the EDA complexes induces a single electron transfer (SET) process to generate aryl radical species for the arylation step. This Review will focus on the state‐of‐the‐art EDA complex‐based arylation strategies utilizing aryl halides, aryldiazonium, diaryliodonium, arylsulfonium and arylphosphonium salts as reactants, published mainly in the last five years.

Dioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation

The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities for synthetic chemistry. However, these strategies often require an inert atmosphere to maintain high efficiency. Herein, we develop an EDA complex photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems and enables aerobic oxygenation reactions through dioxygen activation. The mild oxidation system transfers electrons from the donor to the effective catalytic acceptor upon visible light irradiation, which are subsequently captured by molecular oxygen to form the superoxide radical ion, as demonstrated by the specific fluorescent probe, dihydroethidine (DHE). Furthermore, this visible-light mediated oxidative EDA protocol is successfully applied in the aerobic oxygenation of boronic acids. We believe that this photochemical dioxygen activation strategy enabled by EDA complex not only provides a practical approach to aerobic oxygenation but also promotes the design and application of EDA photocatalysis under ambient conditions.

Aerobic Oxidative Hydroxylation of Arylboronic Acids under Visible-Light Irradiation without Metal Catalysts or Additives.

Phenols are versatile synthetic intermediates and key structural motifs in many natural products and biologically active compounds. We herein report a visible-light-induced aerobic oxidative hydroxylation of arylboronic acids/pinacol esters using air as oxidant and without using any catalysts and base, etc., additives, providing a green entry to a variety of phenols in a highly efficient and concise fashion. This novel reaction is enabled by photoactivation of an electron donor-acceptor complex, in which THF serves as both the solvent and electron donor. DFT studies indicated that the oxidation process involves a concerted hydrogen abstraction transfer from THF and dehydroxylation of boronic acid undergoing spin crossover from triplet to singlet to produce an active peroxoboronic acid intermidiate. Salient merits of this chemistry include broad substrate scope and excellent functional group tolerance, gram-scale synthesis, and versatile late-stage functionalizations as well as the use of air, visible light, and catalyst- and additive-free conditions. This strategy introduces a novel photoreaction mode with the aid of a solvent, offering a succinct and environmentally sustainable route for synthesizing phenols. The strong practicability and highly efficient access to modifying complex biorelevant molecules bode well for the potential applications of this chemistry in pharmaceutical chemistry.

Harnessing the Potential of Electron Donor-Acceptor Complexes and N-Centered Radicals: Expanding the Frontiers of Isoquinoline Derivative Synthesis.

Research on synthesizing nitrogen-containing heterocyclic scaffolds is important because these structures are commonly found in Nature, such as in the alkaloids' family. In our study, we propose a new method to synthesize the isoquinoline core using an electron donor-acceptor (EDA) complex strategy. Our mechanistic investigations have confirmed that our synthesis process operates through an EDA mechanism, which is not extensively discussed in the literature, particularly regarding its applications on alkynyl substrates. This EDA strategy has proven to be a simple and straightforward way to produce isoquinoline scaffolds and their derivatives without the need for metal catalysts.