Cross-dehydrogenative Coupling Research Articles

Porous polyselenoviologen with long-lived charge separated states and highly cyclic stability for heterogeneous photocatalytic reaction and hydrogen production

A highly stable heterogeneous photocatalyst, porous polyselenoviologen (POP-SeV2+), was successfully synthesized via SN2 reaction. Compared to the monomer, POP-SeV2+ exhibited strong visible-light absorption, enhanced electron acceptor property, and prolonged lifetime of radical cations. Simultaneously, the femtosecond transient absorption (fs-TA) illustrated that the formation of tetrahedral multi-cationic structure is conducive to the rapid generation of molecular excited states and extending the duration of charge-separated states. Due to its remarkable characteristics, the POP-SeV2+ was employed as a photocatalyst for visible-light-induced cross-dehydrogenative coupling (CDC) reactions with a highly efficient yield (82 %). Additionally, its utilization was further extended to the hydrogen generation, demonstrating remarkable outcomes such as a high rate of H2 generation (300 μmol·h−1·g−1), and an apparent quantum yield (0.13 %). Notably, POP-SeV2+ displayed great stability and reusability in the photocatalytic process, which can distinguish it from those soluble SeV2+-based photocatalysts. The catalytic efficiency of POP-SeV2+ remained virtually unaffected even after undergoing several recycling cycles, which not only achieved the complete heterogeneous photocatalysis of SeV2+-based systems for the first time but also provided a new strategy to improve the application effect of viologen derivatives in solar energy conversion and utilization.

Pincer manganese-catalyzed C–H phosphinomethylation of indoles and naphthols with methanol as C1 block

We here report a facile manganese-catalyzed three-component phosphinomethylation of indoles and naphthols using methanol as a sustainable C1 source and an acceptorless dehydrogenation strategy. A set of indoles, naphthols, and phosphines with different substituents could efficiently undergo the acceptorless dehydrogenative cross-coupling and furnish the corresponding C–H phosphinomethylated indoles and naphthols in moderate to good yields. Mechanistic studies indicate that this transformation proceeds with the dehydrogenation of methanol to form a formaldehyde-coordinated manganese species as the key intermediate.

Double C-H Amination of Naphthylamine Derivatives by the Cross-Dehydrogenation Coupling Reaction.

A high-efficiency tandem process has been developed for the formation of two C-N bonds through a cross-dehydrogenative coupling (CDC) amination of spiro[acridine-9,9'-fluorene]s (SAFs) with amines. This method offers a strategically innovative and atom-economical approach to obtaining diamine-substituted SAFs. Notably, the approach eliminates the need for metal catalysts and other additives, relying solely on O2 as the oxidant. A self-activation mechanism has been proposed to elucidate the effective double amination in the CDC process.

Pyrazine-based supramolecular photosensitizing assemblies as type I photosensitizers for high-efficiency photooxidation reactions

Donor-acceptor thermally activated delayed fluorescent (TADF) materials have been widely used in photocatalytic reactions as organic photosensitizers. However, the construction of TADF photosensitizers via a supramolecular self-assembly approach with the regulation of reactive oxygen species (ROS) is still a big challenge. In this study, a TADF molecule 4,4'-(6-(pyridin-4-yl)quinoxaline-2,3-diyl)bis(N,N-diphenylaniline) (TPA-PQ) by incorporating triphenylamine (TPA) act as donor and 6-(pyridin-4-yl)quinoxaline (PQ) act as an acceptor was designed and synthesized, which exhibited excellent TADF property and strong intramolecular charge transfer. Meanwhile, the TPA-PQ can not only self-assemble to form nanofiber structure in mixed solvent of H2O and THF, but also can be used as a type I photosensitizer to selectively produce superoxide anion radicals (O2•–). More interestingly, the ROS generated from TPA-PQ can be used as photocatalysts for the oxidative hydroxylation of arylboronic acids and aerobic cross dehydrogenation coupling (CDC) reactions with high yields of 92 % and 88 %, respectively. This study presents an innovative and eco-friendly approach to utilize TADF supramolecular structures for the purpose of conducting photocatalyzed organic reactions.

Pd-catalysed regioselective cross dehydrogenative coupling of quinazolinones with aromatic carboxylic acids

A simple protocol for a regioselective cross dehydrogenative reaction of 2-aryl-quinazolinones with different phenyl carboxylic acids was developed using a palladium catalyst facilitated by CH activation. Simple and readily accessible aromatic carboxylic acids were utilized as a source of benzoxylate. A one-pot method proceeded with great regioselectivity and offered mono benzoxylation product with moderate to excellent yield.

Direct C−H Alkylation of Naphthoquinone with Acetone and 1,3‐Dicarbonyl Compounds via Radical Cross Dehydrogenation Coupling

AbstractA direct C−H alkylation of naphthoquinones with acetone and 1,3‐dicarbonyl compounds was developed to construct C−C bonds of alkyl‐substituted naphthoquinone derivatives. It proceeded through an oxidative radical cross dehydrogenation coupling process under simple and mild conditions. This method provides a facile and efficient route for synthesis of functionalized naphthoquinones from readily available feedstocks.

Tunable multicolor supramolecular assemblies based on phosphorescence cascade energy transfer for photocatalytic organic conversion and anti-counterfeiting

Making full use of the captured energy by phosphorescence light-harvesting systems (PLHSs) and the tunable photoluminescence in energy transfer process to realize the multiple applications is still the challenge of PLHSs research. In this study, we have successfully constructed a highly effective PLHS with tunable multicolor luminescence and efficient conversion of photosensitizer types, which can further be used in photocatalytic organic conversion, information anti-counterfeiting and storage. The supramolecular polymer of BDBP-CB[8], which is generated by cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)-pyridine derivative (BDBP), realizes a phosphorescence emission and a change in luminescence color. Notably, white light emission was achieved and the logic gate systems were constructed utilizing the application of adjustable luminescence color. More interestingly, PLHS can be constructed by employing BDBP-CB[8] as energy donors, Sulforhodamine 101 (SR101) and Cyanine5 (Cy5) as energy acceptors, which results in a remarkably tunable multicolor photoluminescence to achieve the information storage. Furthermore, we have also found that BDBP-CB[8] can serve as type II photosensitizer for the effective production of singlet oxygen (1O2) during the photooxidation process of styrene in aqueous environments, attaining a remarkable output rate reaching as high as 89 %. Particularly, compared with 1O2 produced by type II photosensitizer BDBP-CB[8], the construction of PLHS can effectively convert type II photosensitizer to type I photosensitizer and efficiently generate superoxide anion radical (O2•−), which can be used for photocatalytic cross-dehydrogenative coupling (CDC) reaction in the aqueous solution with a yield of 90 %. Thus, we have created a PLHS that not only achieves tunable multicolor emission for information anti-counterfeiting and storage, but also realizes the conversion of reactive oxygen species (ROS) for different types photocatalytic oxidation reactions.

N-Bu4NI/K2S2O8-MEDIATED C-N COUPLING BETWEEN ALDEHYDES AND AMIDES.

n-Bu4NI/K2S2O8 mediated C-N coupling between aldehydes and amides is reported. A strong electronic effect is observed on the aromatic aldehyde substrates. The transformylation from aldehyde to amide takes place exclusively when an aromatic aldehyde bears electron-donating groups at either the ortho or para position of the formyl group, while the cross-dehydrogenative coupling dominates in the absence of these groups. Both the density functional theory (DFT) thermochemistry calculations and experimental data support the proposed single electron transfer mechanism with the formation of an acyl radical intermediate in the cross-dehydrogenative coupling. The n-Bu4NI/K2S2O8 mediated oxidative cyclization between 2-aminobenzamide and aldehydes is also reported, with four quinazolin-4(3H)-ones prepared in 65-99% yields.

RhRu Bimetallic Oxide Cluster Catalysts for Cross-Dehydrogenative Coupling of Arenes and Carboxylic Acids.

Noble-metal-based bimetallic oxide clusters are promising novel catalysts. In this study, we developed carbon-supported RhRu bimetallic oxide clusters (RhRuOx/C) with a mean diameter of 1.2 nm, which showed remarkable catalytic activity for the cross-dehydrogenative coupling (CDC) of arenes and carboxylic acids with O2 as the sole oxidant. RhRu bimetallic oxide cluster formation was confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and synchrotron X-ray absorption spectroscopy. Kinetic isotope and substituent effects indicated that arene C-H bond cleavage was the rate-determining step and proceeded via electrophilic concerted metalation-deprotonation mechanism, with a carboxylate as an internal base. Density functional theory calculations supported the proposed mechanism and indicated that the active center for C-H bond activation was Rh(V) rather than Rh(III), while Ru enhanced the electrophilicity of the Rh(V) site by decreasing the negative charge of the surrounding oxygen atoms. Electron-rich arenes showed relatively high reactivity for the RhRuOx/C-catalyzed CDC reaction, and both aliphatic and aromatic carboxylic acids were applicable to the reaction. The RhRuOx/C catalyst is promising for the CDC reaction of arenes and carboxylic acids to produce aryl esters. This work promotes the development of noble-metal-based bimetallic oxide clusters for C-H bond activation reactions.

Oxidative Tandem Cyclization of Aromatic Acids with (Benzo)thiophenes: One-Pot Access to Planar Sulfur-Containing Polycyclic Heteroarenes for Lipid-Droplet-Targeted Probes.

The efficient construction of π-conjugated polycyclic heteroarenes represents a significant task in the field of functional materials. A one-step oxidative tandem cyclization of aromatic acids with (benzo)thiophenes was developed to access planar sulfur-containing polycyclic heteroarenes. This protocol undergoes intermolecular cross-dehydrogenative coupling followed by intramolecular Friedel-Crafts acylation and provides a facile pathway to planar polycyclic compounds from inexpensive reactants. The synthesized heteroarenes serving as lipid-droplet-targeted probes exhibit outstanding performance with favorable biocompatibility and photostability.

Phenotellurazine redox catalysts: elements of design for radical cross-dehydrogenative coupling reactions.

Redox active phenotellurazine catalysts have been recently utilized in two different cross-dehydrogenative coupling reactions. In this study, we revisit the design of the phenotellurazine redox catalysts. In particular, we investigate the level of cooperativity between the Te- and N-centers, the effect of secondary versus tertiary N-centers, the effect of heterocyclic versus non-heterocyclic structures, and the effect of substitution patterns on the redox catalytic activity.

Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp3)-H bonds enabled by organocatalysis

An efficient and scalable electrochemical asymmetric protocol with metal-free catalysts and even without additional oxidants for the cross-dehydrogenative coupling reaction (CDC) of two C(sp3)-H bonds is reported. A series of aldehydes including natural products and various substrates containing C(sp3)-H bonds including xanthenes, acridines, cycloheptatrienes and even diarylmethane have been shown to undergo asymmetric CDC to afford a series of carbon-carbon bond coupling products with up to 94% yield and 98% ee. Mechanistic studies such as radical clock experiment suggest that the reaction proceeds via nucleophilic attack by enamine under electrochemical conditions.

Cross-Dehydrogenative Couplings to Access C4-Disubstituted Dihydroquinazolines

Cross-Dehydrogenative Couplings to Access C4-Disubstituted Dihydroquinazolines

A dual strategy of direct C(sp3)-H sulfonamidation by cross-dehydrogenative coupling and oxidative hydroxylation-condensation

Sulfonamides are an important class of structures, although their construction is a major challenge for the synthetic community. Herein, we report a dual strategy for direct C(sp3)-H sulfonamidation, namely, a combined cross-dehydrogenative coupling and oxidative hydroxylation/condensation. This strategy, catalyzed by n-tetrabutylammonium bromide, reduced oxidant loading to 1.0 equivalent. The reaction was mediated by MgSO4•2H2O, which improved sulfonamide yields. The practicability of this method was highlighted by its broad substrate scope, mildness, site-selectivity, gram-scalability, and capability for late-stage functionalization of drug molecules.

A Robust Pyrazolate Metal-Organic Framework for Efficient Catalysis of Dehydrogenative C-O Cross Coupling Reaction.

Construction of robust heterogeneous catalysts with atomic precision is a long-sought pursuit in the catalysis field due to its fundamental significance in taming chemical transformations. Herein, we present the synthesis of a single-crystalline pyrazolate metal-organic framework (MOF) named PCN-300, bearing a lamellar structure with two distinct Cu centers and one-dimensional (1D) open channels when stacked. PCN-300 exhibits exceptional stability in aqueous solutions across a broad pH range from 1 to 14. In contrast, its monomeric counterpart assembled through hydrogen bonding displays limited stability, emphasizing the role of Cu-pyrazolate coordination bonds in framework robustness. Remarkably, the synergy of the 1D open channels, excellent stability, and the active Cu-porphyrin sites endows PCN-300 with outstanding catalytic activity in the cross dehydrogenative coupling reaction to form the C-O bond without the "compulsory" ortho-position directing groups (yields up to 96%), outperforming homogeneous Cu-porphyrin catalysts. Moreover, PCN-300 exhibits superior recyclability and compatibility with various phenol substrates. Control experiments reveal the synergy between the Cu-porphyrin center and framework in PCN-300 and computations unveil the free radical pathway of the reaction. This study highlights the power of robust pyrazolate MOFs in directly activating C-H bonds and catalyzing challenging chemical transformations in an environmentally friendly manner.

Two Different Three-Dimensional Uranium-Containing Polymolybdates Based on Zn(II) for the Heterogeneous Catalytic Construction of C-N Bond.

The introduction of transition metal (TM) ions into polyoxometalates (POMs) cannot only bring about interesting structural diversities but also enable changes in properties. However, TM-containing Silverton-type polyoxomolybdates are still lacking in terms of structural diversity and application development. Herein, two Zn(II)-containing Silverton-type {UMo12O42}-based polyoxomolybdates, H1.89Na4.11(H2O)9Zn[UMo12O42]·4.5H2O (Zn-1) and H1.8Na4.2(H2O)12Zn[UMo12O42] (Zn-2) were hydrothermally synthesized, demonstrating a practical strategy to assembly of TM-containing Silverton-type POMs. Zn-1 is proven to be an excellent and recyclable heterogeneous catalyst in cross-dehydrogenation coupling of 1,4-naphthoquinones with amines reactions, and a series of 2-amino-1,4-naphthoquinones with potential medicinal value have been constructed.

Organoselenium-Catalyzed C2,3-Diarylation of N-H Indoles.

An organoselenium-catalyzed C2,3-diarylation of unprotected N-H indoles with electron-rich aromatics has been developed. This one-pot multicomponent tandem cross-dehydrogenation coupling reaction allows for the incorporation of two different aromatic groups to indoles. More importantly, this approach offers significant advantages, including a high atom and step economy, eliminating the need for prepreparation of the reaction substrates, streamlining the synthetic process and enhancing its practicality. Overall, this organoselenium-catalyzed C2,3-diarylation reaction presents an efficient and versatile strategy for the functionalization of indole derivatives.

Oxidative C–N Bond Formation of Isochromans Using an Electronically Tuned Nitroxyl Radical as Catalyst

AbstractThe cross-dehydrogenative coupling between isochromans and nucleophiles using an electronically tuned nitroxyl radical catalyst, which effectively promotes the oxidation of benzylic ethers, has been investigated. Using sulfonamides as a nucleophile, modification of isochromans via oxidative C–N bond formation has been achieved at ambient temperature.

Palladium-Catalyzed Weak Chelation-Assisted Site-Selective C-H Arylation of N-Aryl Pyridones via 2-fold C-H Activation.

Palladium-catalyzed weak chelation-assisted oxidative cross-dehydrogenative coupling of arenes has been accomplished. The use of medicinally important pyridones as the intrinsic directing group, regioselectivity, 2-fold C-H activation, and late-stage modification of bioactive compounds are the important practical features.

Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst

Cross-dehydrogenative coupling of C(sp3)-H bonds is an ideal approach for C(sp3)-C(sp3) bond construction. However, conventional approaches mainly rely on a single activation mode by either stoichiometric oxidants or electrochemical oxidation, which would lead to inferior selectivity in the reaction between similar C(sp3)-H bonds. Herein we describe our development of a paired electrocatalysis strategy to access an unconventional selectivity in the cross-dehydrogenative coupling of alcoholic α C(sp3)-H with allylic (or benzylic) C-H bonds, which combines hydrogen evolution reaction catalysis with hydride transfer catalysis. To maximize the synergistic effect of the catalyst combinations, a HER catalyst pentacoordinated Co-salen is disclosed. The catalyst displays a large redox-potential gap (1.98 V) and suitable redox potential. With the optimized catalyst combination, an electrochemical cross-dehydrogenative coupling protocol features unconventional chemoselectivity (C-C vs. C-O coupling), excellent functional group tolerance (84 examples), valuable byproduct (hydrogen), and high regio- and site-selectivity. A plausible reaction mechanism is also proposed to rationalize the experimental observations.